KR102024917B1 - Vapour deposition method for fabricating lithium-containing thin film layered structures - Google Patents

Abstract

The vapor deposition method for preparing a multi-layer thin film structure provides a vapor source of each component element of a compound intended for a first layer and a compound intended for a second layer, the vapor sources being at least a lithium source, An oxygen source, a source or sources of one or more glass-forming elements, and a source or sources of one or more transition metals; Heating the substrate to a first temperature; Simultaneously depositing component elements from at least lithium, oxygen, and one or more transition metals on a heated substrate, wherein the component elements react on the substrate to form a layer of crystalline lithium-containing transition metal oxide compound; ; Heating the substrate to a second temperature within the temperature range of substantially 170 ° C. or less from the first temperature; And simultaneously depositing component elements from at least lithium, oxygen, and one or more vapor sources of glass onto the heated substrate, wherein the component elements form a substrate to form a layer of amorphous lithium-containing oxide or oxynitride compound. Reacts in phase.

Description

VAPOUR DEPOSITION METHOD FOR FABRICATING LITHIUM-CONTAINING THIN FILM LAYERED STRUCTURES

The present invention relates to a method for producing thin film layer structures comprising lithium compounds by vapor deposition.

Deposition of materials in thin film form is of great interest for many applications of thin films, and a variety of different deposition techniques are known. Various techniques are nearly suitable for certain materials, and the quality, composition and properties of the resulting thin film typically depend largely on the process used for its formation. As a result, much research has been devoted to developing deposition processes that can produce thin films suitable for specific applications.

An important application of thin film materials is in solid state thin film cells or batteries, such as lithium ion cells. Such batteries consist of at least three components. Two active electrodes (anode and cathode) are separated by an electrolyte. Each of these components is formed as a thin film and deposited sequentially on the support substrate. Additional components may also be provided, such as current collectors, interface modifiers, and encapsulations. In manufacturing, the components can be deposited, for example, in the order of cathode current collector, cathode, electrolyte, anode, anode current collector and encapsulation. The structure of these batteries places additional burdens on the deposition processes of the individual components since the manufacture of a particular layer should not have a detrimental effect on any layers already deposited.

In a lithium ion battery example, the anode and cathode can reversibly store lithium. Other requirements for anode and cathode materials are high gravimetric and volumetric storage capacities that can be achieved with low mass and volume of material, but the number of lithium ions stored per unit should be as high as possible. The materials must also exhibit acceptable electron and ion conduction so that ions and electrons can move through the electrodes during the battery charge and discharge process.

Otherwise, the anode, cathode and electrolyte require different properties. The cathode should provide reversible lithium intercalation at high potentials, while the anode should provide reversible lithium intercalation at low potentials.

The electrolyte must have an extremely low electrical conductivity to physically separate the anode and cathode, to prevent short circuit of the battery. However, in order to enable reasonable charge and discharge characteristics, the ionic conductivity of the material should be as high as possible. In addition, the material must be stable during the cycling process and must not react with either the cathode or the anode.

The manufacture of solid state batteries poses a variety of challenges. In particular, reliable and efficient techniques for producing materials suitable for use as cathodes are of great interest. For some popular cathode materials, the cathode layer of the battery is required to have a crystalline structure to provide the required properties described above. However, depositing a quality crystalline cathode layer in a manner compatible with subsequent steps in the manufacture and processing of a complete battery is often a problem. Electrolyte materials are often required to be amorphous or desired to be amorphous, and additional challenges are solids with sufficiently high ionic conductivity, low electron conductivity, and low mechanical stress resulting from the required electrochemical cycling and renewable high yield generation methods. Identification of the electrolytes.

Many different methods of depositing components of thin film batteries are known. Synthetic routes to thin films commonly referred to using the generic term 'physical vapor deposition' are described by pulsed laser deposition (Tang, SB, et al., J. Solid State Chem., 179 (12), (2006), 3831-3838), flash evaporation (Julien, CM and GA Nazri, Chapter 4. Materials for electrolyte: Thin Films, in Solid State Batteries: Materials Design and Optimization (1994)), sputtering and thermal deposition do.

Of these, sputtering is the most extensive deposition technique. In this way the target of a particular composition is sputtered using a plasma formed over the target and the resulting vapor condenses on the substrate to form a thin film. Sputtering involves the deposition of materials directly from a target. The sputter product is variable and may contain dimers, trimers or higher order particles (Thornton, JA and JE Greene, Sputter Deposition Processes, in Handbook of Deposition Technologies for films and coatings, RF Bunshah , Editor 1994, Noyes Publications). The deposition rate, composition, morphology, crystallinity and performance of the thin films is determined by the complex relationship with the sputtering parameters used.

Sputtering may be undesirable in that it is difficult to predict the effects of various sputtering parameters on the properties and performance of the deposited material. In part this is due to the confounding of film properties and deposition parameters. The deposition rate, composition, morphology, crystallinity and performance of the sputtered thin films are determined by the complex relationship with the sputtering parameters used. Therefore, it can be very difficult to change individual parameters (eg, concentration, deposition rate or crystallinity of a single element) of the sputtered film without affecting other properties of the film. This results in difficulties in achieving the composition of interest, which makes the optimization of the membrane and therefore the optimization of the properties of any intended battery or other problematic thin film device.

박막들의 표면 형태학은 거친 것이 주의되었고, 상향으로 30 nm로부터의 사이즈들을 가진 그레인(grain)들의 형성은 증착 온도에 좌우된다((Wang et al. Electrochimica Acta 102 (2013) 416-422). 표면 거칠기는 고체 상태 배터리 같은 층진 박막 구조들에서 매우 바람직하지 않고, 여기서 임의의 큰 돌출하는 피처(feature)들은 인접 층 내로 또는 심지어 인접 층을 통하여 잘 연장될 수 있다.Pulsed laser deposition (PLD) technology shares many properties with sputtering due to the use of compositionally unique targets and the use of high energies. In addition, this route often produces very rough samples, which is also a problem with sputtering. Prepared by PLD

It was noted that the surface morphology of the thin films is rough, and the formation of grains with sizes from 30 nm upwards depends on the deposition temperature (Wang et al. Electrochimica Acta 102 (2013) 416-422). Is very undesirable in layered thin film structures such as solid state batteries, where any large projecting features can extend well into or even through adjacent layers.

(LMO, 리튬 망간 산화물) 및

(Julien, C.M. and G.A. Nazri, Chapter 4. Materials for electrolyte: Thin Films, in Solid State Batteries: Materials Design and Optimization (1994)) 같은 재료들에 대한 배터리 컴포넌트들의 합성에서 보여진다. 이 예에서 입자 에너지들은 스퍼터링시 직면되는 에너지들보다 훨씬 낮고, 이는 클러스터 형성을 방지할 수 있고, 표면 거칠기를 감소시킬 수 있고 그리고 부드럽고, 손상되지 않은 표면들을 제공할 수 있다. 그러나, 소스와 결과적인 박막 사이의 컴포지션의 변동 같은 문제들은 화합물 증착 타겟들(스퍼터링 및 PLD를 포함함)로 시작하는 모든 루트들에 공통이다. 게다가, 기판 온도와 증착된 막의 컴포지션 사이의 관계가 존재하고 또 다시 파라미터들의 교락으로 인해 재료 성능을 최적화하는데 어려움들을 초래한다는 것이 주의된다.Deposition of thin films from thermal deposition of compound sources

(LMO, lithium manganese oxide) and

(Julien, CM and GA Nazri, Chapter 4. Materials for electrolyte: Thin Films, in Solid State Batteries: Materials Design and Optimization (1994)) are shown in the synthesis of battery components for such materials. Particle energies in this example are much lower than the energies encountered upon sputtering, which can prevent cluster formation, reduce surface roughness and provide smooth, undamaged surfaces. However, problems such as variations in composition between the source and the resulting thin film are common to all routes starting with compound deposition targets (including sputtering and PLD). In addition, it is noted that there is a relationship between the substrate temperature and the composition of the deposited film, which again results in difficulties in optimizing material performance due to the entanglement of the parameters.

(X = I, Cl, SO4 및 n = 1,2)를 합성하기 위한 시도를 시사하지만, 어떠한 결과들로 보고되지 않고 저자들은 "이 기술을 구현하는데 어려움들이 산소 펌핑을 강화하고, 시스템의 가열된 부분들과 높은 산소 반응성을 회피하고, 그리고 표면상에서 산소 반응들을 강화하기 위하여 산소 단원자 소스를 이용 가능하게 하는데 있다"는 것을 언급한다. An alternative is thermal deposition directly from the elements, but this is rare. Julien and Nazri (Chapter 4. Materials for electrolyte: Thin Films, in Solid State Batteries: Materials Design and Optimization (1994))

Suggests attempts to synthesize (X = I, Cl, SO4 and n = 1,2), but no results are reported and the authors report that "difficulties in implementing this technique enhance oxygen pumping and heating the system. To avoid high oxygen reactivity and to enhance the oxygen reactions on the surface. ”

-예 1 및 질소 도핑

-예 6)의 합성이 개시된다. 증착된 재료들은 비정질이고, 따라서 어닐링은 각각 LFP 및 LMP에 대해 500℃ 및 600℃의 온도들에서 캐소드 재료들을 결정화하기 위하여 사용된다. 비록 이런 작업이 박막 셀을 생성하기 위한 3개의 기본 빌딩 블록들 중 2개를 보여주지만, 동작 셀을 보여주지 않는다. 게다가, 이런 작업에서 보여진 이온 전도율들은 셀이 실온에서 올바르게 기능하기에는 너무 낮다. 실온에서 1 x 10^-6 S cm^-1의 전도율이 만족스러운 성능을 위하여 요구되지만, 이것이 보여지지 않았다는 것은 널리 알려져 있다.Previously, we have shown the synthesis of phosphorus-containing materials suitable for some thin film battery components directly from the constituent elements (WO 2013/011326; WO 2013/011327). However, the complexity of this process is the use of crackers to break down phosphorus to enable the formation of phosphates. Cathode (lithium iron phosphate (LFP) -example 5, lithium manganese phosphate (LMP) -example 7) and electrolyte materials ((

Example 1 and nitrogen doping

The synthesis of Example 6) is initiated. The deposited materials are amorphous, so annealing is used to crystallize the cathode materials at temperatures of 500 ° C. and 600 ° C. for LFP and LMP, respectively. Although this work shows two of the three basic building blocks for creating a thin film cell, it does not show the working cell. In addition, the ionic conductivities shown in this work are too low for the cell to function properly at room temperature. It is well known that a conductivity of 1 × 10 ⁻⁶ S cm ⁻¹ at room temperature is required for satisfactory performance, but this has not been shown.

(LMO) 및

(LMNO) 같은 기술 캐소드 재료들의 상태는 최적 이온 전도율을 달성하기 위하여 결정질 상태에 있을 것이 요구된다. 이것은 낮은 온도 증착 다음 높은 기판 온도들에서 포스트(post) 어닐링 또는 증착에 의해 달성될 수 있다. 낮은 기판 온도들(250℃ 미만)에서 증착된 캐소드들은 종종 불충분한 결정질이고, 이는 감소된 성능을 초래한다. 그러므로, 추가 결정화 단계가 요구되고; 이것은, 비록 이 단계가 막에서 리튬 결핍을 초래할 수 있지만(Singh et al. J. Power Sources 97-98 (2001), 826-831), 포스트-증착, 높은 온도 어닐링에 의해 통상적으로 달성된다. 가열된 기판에 RF-스퍼터링에 의해 증착된 LMO의 샘플들은 250℃의 초기 결정화 온도를 가지는 것으로 발견되었지만, 200℃ 미만의 기판 온도를 사용하여 성장될 막들은 X-선 비정질인 재료들과 동일한 넓고 분산된 XRD 패턴을 나타냈다(Jayanth et al. Appl Nanosci. (2012) 2:401-407).

(LMO) and

The state of technical cathode materials such as (LMNO) is required to be in a crystalline state to achieve optimal ion conductivity. This may be accomplished by post annealing or deposition at high substrate temperatures following low temperature deposition. Cathodes deposited at low substrate temperatures (less than 250 ° C.) are often insufficient crystalline, resulting in reduced performance. Therefore, an additional crystallization step is required; This is typically accomplished by post-deposition, high temperature annealing, although this step can lead to lithium deficiency in the membrane (Singh et al. J. Power Sources 97-98 (2001), 826-831). Samples of LMO deposited by RF-sputtering on heated substrates were found to have an initial crystallization temperature of 250 ° C., but films to be grown using substrate temperatures below 200 ° C. were broad and the same as those of X-ray amorphous materials. Dispersed XRD patterns were shown (Jayanth et al. Appl Nanosci. (2012) 2: 401-407).

(LMNO) 박막들은 550과 750℃ 사이의 더 높은 기판 온도들에서 PLD를 사용하여 증착된 다음 동일한 온도에서 1시간 동안 포스트 어닐링된다(Wang et al. Electrochimica Acta 102 (2013) 416-422). 이들 같은 높은 기판 온도들을 사용하는 것은 특정 단점들을 가진다. 리튬의 손실은 더 높은 온도들에서 더 크고, 증착된 막과 기판 사이에 재료들의 분산으로 인한 상호 오염의 가능성이 있고, 이는 사용하기 위해 이용 가능한 기판들을 제한한다.Crystalline

(LMNO) thin films are deposited using PLD at higher substrate temperatures between 550 and 750 ° C. and then post annealed for one hour at the same temperature (Wang et al. Electrochimica Acta 102 (2013) 416-422). Using high substrate temperatures such as these have certain drawbacks. The loss of lithium is greater at higher temperatures and there is a possibility of cross contamination due to the dispersion of materials between the deposited film and the substrate, which limits the substrates available for use.

)은 스퍼터링된 박막들을 어닐링함으로써 결정화되었지만, 결과적인 층들은 다결정질이고 50-150 nm 사이의 직경들을 가진 그레인들로 구성된다. 막들은 또한 다수의 불순물 위상들을 포함하는 것으로 도시되었다(Baggetto et al., J Power Sources 211 (2012) 108-118).The process of annealing, which involves exposing the material to high temperatures to crystallize, is potentially applicable whenever the deposited material is insufficient crystalline. The required temperature will depend on the material, but is typically at least 500 ° C. and can be significantly higher, and the resulting crystalline layer may have poor quality. As an example, the cathode material lithium manganese nickel oxide (LMNO;

) Was crystallized by annealing the sputtered thin films, but the resulting layers were polycrystalline and consist of grains with diameters between 50-150 nm. The films have also been shown to contain multiple impurity phases (Baggetto et al., J Power Sources 211 (2012) 108-118).

으로 만들어진 캐소드들 같은) 및 비정질 전해질들(LiPON 같은)을 요구한다. 이런 요건은, 전해질의 결정화를 회피하기 위하여, 일반적으로 전해질 층의 증착 전에 캐소드를 어닐링하는 것이 필요하다는 것을 의미한다. 이런 단계는 충분한 결정화를 제공하기 위하여 시간 및 에너지 둘 다를 요구한다. 게다가, 졸-겔 및 고체 상태 합성을 위한 하나 또는 그 초과의 높은 온도 프로세싱 단계들(예컨대,

: PLD 동안 550-750℃(Wang, Y., et al., Electrochimica Acta, (2013), 102(0), 416-422) 및 750-800℃에서 다수의 어닐링(Zhong, Q., et al., J. Electrochem. Soc., (1997), 144(1), 205-213)은 통상적으로 요구되고, 이에 의해 그런 높은 온도 프로세싱과 호환 가능한 것들로 기판 같은 컴포넌트들이 제한된다. 부가적으로 그런 프로세스는, 이미 증착된 임의의 비정질 전해질이 또한 어닐링되어, 결정화가 유발되기 때문에, 셀들의 스택(stack)을 생성하기 위하여 기존 셀상에 부가적인 셀의 증착을 방지한다. 그런 결정화는 기술적 전해질(LiPON) 상태의 이온 전도율의 극적 감소를 유발하는 것으로 알려져 있다. 결정질(LiPON)의 전도율은 비정질 재료의 전도율보다 7배만큼 작을 수 있다는 것이 알려져 있다(Bates et al. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. Journal of Solid State Chemistry 1995, 115, (2), 313-323). 그런 높은 온도 프로세싱과 연관된 추가 문제들은 개별 층들의 박리(delamiantion) 및 크랙킹(cracking)을 포함한다.In addition, annealing is of undesirable complexity and is particularly problematic in the manufacture of finished batteries or other layered devices. As discussed, solid-state batteries based on the state of the art materials are crystalline electrodes (

Cathodes) and amorphous electrolytes (such as LiPON). This requirement means that in order to avoid crystallization of the electrolyte, it is generally necessary to anneal the cathode prior to the deposition of the electrolyte layer. This step requires both time and energy to provide sufficient crystallization. In addition, one or more high temperature processing steps (eg, for sol-gel and solid state synthesis)

: Multiple annealing at 550-750 ° C. (Wang, Y., et al., Electrochimica Acta, (2013), 102 (0), 416-422) and 750-800 ° C. during PLD (Zhong, Q., et al. , J. Electrochem. Soc., (1997), 144 (1), 205-213 are commonly required, thereby limiting components such as substrates to those compatible with such high temperature processing. In addition, such a process prevents the deposition of additional cells on existing cells to create a stack of cells since any amorphous electrolyte already deposited is also annealed to cause crystallization. Such crystallization is known to cause a dramatic decrease in the ionic conductivity of the technical electrolyte (LiPON) state. It is known that the conductivity of crystalline (LiPON) can be 7 times smaller than that of amorphous materials (Bates et al. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. State Chemistry 1995, 115, (2), 313-323). Additional problems associated with such high temperature processing include delamiantion and cracking of the individual layers.

를 보여줬다.

의 경우에서, O₂ 이온들의 빔이 활용되었다. 이런 산소 빔은

의 결정화 및 화학양론 둘 다를 제어하는 2개의 기능들을 가지는 것으로 언급된다(EP 1,305,838). 이온들의 빔은 박막들의 준비시 직면되는 3개의 문제들을 처리한다 - 컴포지셔널 제어, 밀집한 막들의 준비 및 결과적인 막들의 결정화. 그러나, 이온 빔은 복잡한 양상의 프로세스이다.Techniques have been proposed to address these issues. For example, it has been shown that it is possible to deposit crystalline films in place by providing a focused beam of ions (WO 2001/73883). In this case the adsorbent atoms of the cathode material (in this case defined as particles, molecules or ions of the material not yet formed in the structure or film) are deposited on the substrate, while the second flux of ions Energized the cathode material. The flux of the second material provided energy to the first material to assist in the growth of the desired crystalline material. This is the cathode

Showed.

In the case, a beam of O ₂ ions was utilized. This oxygen beam

It is said to have two functions that control both crystallization and stoichiometry of (EP 1,305,838). The beam of ions addresses three problems encountered in the preparation of thin films-compositional control, preparation of dense films and crystallization of the resulting films. However, ion beams are a complex aspect of the process.

및

같은 결정질 재료들은 일반적으로 우수한 이온 전도율(

의 경우에서 예컨대

까지)를 나타내고 따라서 전해질들에 대해 우수한 후보인 것으로 나타난다. 그러나, 이들 재료들은, 배터리 시스템들에 적용될 때 문제들을 제시한다. 산화물들(LLTO, 티오-LISICON 및 NASICON-타입)의 경우에 전해질 내의 전이 금속들은 환원하기 쉽고, 이는 재료가 전자 전도율을 나타내고 따라서 배터리를 단락시키게 한다.

같은 황화물 시스템들은 극히 높은 전도율들을 제시하지만 공기 및 물에 노출될 때 분해되기 쉽고, 이는 유독성

의 방출 및 성능의 저하를 유발한다. 게다가, 산화물 및 황화물 결정질 전해질들 둘 다는 극히 높은 프로세싱 온도들을 요구한다. 이들 이유들 때문에, 결정질 전해질들은 상업적 박막 배터리 시스템들에서 활용되지 않았다.Returning to the electrolyte component of the battery, both crystalline and non-crystalline (amorphous) electrolyte materials were considered. Lithium Lanthanum Titanate (LLTO), Thio-LISICON, MASICON-Type

And

Such crystalline materials generally have good ionic conductivity (

In the case of

) And therefore appear to be a good candidate for electrolytes. However, these materials present problems when applied to battery systems. In the case of oxides (LLTO, thio-LISICON and NASICON-type), the transition metals in the electrolyte are easy to reduce, which causes the material to exhibit electron conductivity and thus short the battery.

The same sulfide systems present extremely high conductivity but are prone to degradation when exposed to air and water, which is toxic.

Causes the release and degradation of performance. In addition, both oxide and sulfide crystalline electrolytes require extremely high processing temperatures. For these reasons, crystalline electrolytes have not been utilized in commercial thin film battery systems.

두께 미만이면, 이것은 허용 가능한 것으로 결정되었다(Julien, C. M.; Nazri, G. A., Chapter 1. Design and Optimisation of Solid State Batteries. In Solid State Batteries: Materials Design and Optimization, 1994). LiPON은

의 허용 가능 이온 전도율을 가지며 공기 및 사이클링될 때 리튬에 대해 안정된 것으로 보여졌다. 제조의 용이성과 결합되어 이들 이유들 때문에, 이는 고체 상태 배터리들의 제 1 세대에서 널리 채택되었다(Bates, J. B.; Gruzalski, G. R.; Dudney, N. J.; Luck, C. F.; Yu, X., Rechargeable Thin Film Lithium Batteries. Oak Ridge National Lab and Solid State Ionics 1993; US 5,338,625). 이들 전해질들의 비정질 성질은 그들의 성능에 중요하고; 결정질 LiPON은 비정질 재료보다 7배 낮은 이온 전도율을 가진다. 그러나, 비정질 LiPON은 표준 합성 기술들을 사용하여 LMO(

, 리튬 망간 산화물) 및 LMNO(

, 리튬 망간 니켈 산화물) 같은 캐소드 재료들을 어닐링하기 위하여 통상적으로 필요한 온도보다 낮은 온도들에서 결정화할 것이고, 이에 의해 이들 재료들을 포함하는 박막 배터리의 제조가 복잡해진다.Amorphous electrolytes such as lithium phosphorus oxynitride (LiPON), lithium silicate and lithium borosilicate exhibit much lower levels of ionic conductivity. Although the optimum conductivity of these materials is at least twice lower than that of crystalline materials, the electrolyte

If less than this, it was determined to be acceptable (Julien, CM; Nazri, GA, Chapter 1. Design and Optimization of Solid State Batteries. In Solid State Batteries: Materials Design and Optimization, 1994). LiPON

It has been shown to have an acceptable ionic conductivity of and is stable to lithium when cycled with air. For these reasons combined with ease of manufacture, it has been widely adopted in the first generation of solid state batteries (Bates, JB; Gruzalski, GR; Dudney, NJ; Luck, CF; Yu, X., Rechargeable Thin Film Lithium Batteries Oak Ridge National Lab and Solid State Ionics 1993; US 5,338,625). The amorphous nature of these electrolytes is important for their performance; Crystalline LiPON has 7 times lower ionic conductivity than amorphous materials. However, amorphous LiPON uses LMO (standard synthesis techniques).

, Lithium manganese oxide) and LMNO (

Will crystallize at temperatures lower than those typically required to anneal cathode materials (such as lithium manganese nickel oxide), thereby complicating the manufacture of thin film batteries comprising these materials.

Thus, amorphous electrolytes are of great interest. An alternative to LiPON is amorphous lithium borosilicate. Amorphous lithium borosilicate materials with ionic conductivity similar to LiPON have been produced, but fast quenching is required by methods (Tatsumisago, M .; Machida, N .; Minami, T., Mixed Anion Effect in Conductivity of Rapidly Quenched Li ₄ SiO ₄ -Li ₃ BO ₃ Glasses.Yogyo-Kyokai-Shi 1987, 95, (2), 197-201). This synthesis method results in irregular "splats" of glass, which is not suitable for processing into thin film batteries.Synthesis by sputtering of similar compositions has been attempted on thin films, but they have not been successful. , Resulting in materials with significantly reduced conductivity when compared to rapidly quenched glass (Machida, N .; Tatsumisago, M .; Minami, T., Preparation of amorphous films in the systems Li ₂ O ₂ and Li ₂ OB ₂ O ₃ -SiO ₂ by RF-sputtering and their ionic conductivity.Yogyo-Kyokai-Shi 1987, 95, (1), 135-7).

의 형성을 초래한다. 게다가, 상승된 온도들에서 증착된 재료들의 라만 스펙트라(Raman spectra)는 관심 있는 리튬 붕규산염 위상과 연관된 대역들을 나타내지 못한다. 또한, 결과적인 비정질 리튬 붕규산염은 배터리의 다른 컴포넌트들을 생성 및 프로세싱하기 위하여 요구된 상승된 온도들에 적용될 때, 또는 배터리가 높은 온도에서 사용 동안 결정화할 것이고, 이에 의해 자신의 전해질 품질들이 말살된다.The inventor's previous work (WO 2013/011326; WO 2013/011327) showing the deposition of thin films of phosphate materials from constituent elements suggests that the technique may be possible with other materials such as lithium borosilicate. However, it has been found that the components of lithium borosilicate following the method described for phosphates during use do not produce the desired thin film material. The elements do not react on the substrate in the manner expected from the phosphate operation so that the required compound is not produced. The use of molecular oxygen instead of atomic oxygen overcomes this problem, but the lithium borosilicate phase of interest is only achieved when the substrate temperature is low (room temperature). The deposition of lithium borosilicates utilizing molecular oxygen at elevated temperatures is a crystalline, undesirable phase when deposited on platinum substrates.

Results in the formation of. In addition, the Raman spectra of materials deposited at elevated temperatures do not exhibit bands associated with the lithium borosilicate phase of interest. In addition, the resulting amorphous lithium borosilicate will crystallize when applied to elevated temperatures required to produce and process other components of the battery, or the battery will crystallize during use at high temperatures, thereby destroying its electrolyte qualities. .

Efforts required to overcome these many difficulties in the various deposition processes and complexity involved in developing new materials mean that the majority of thin film batteries are limited to using LiPON as an electrolyte that is deposited as a thin film by sputtering. do.

Clearly, improved methods of making thin films of other electrolyte materials are desired, and there is also a need for an improved and simplified method of depositing crystalline materials suitable for use as electrodes in thin film batteries. Additionally, incompatibilities between the methods for forming crystalline and amorphous materials need to be addressed so that the fabrication and performance of thin film batteries and other layered thin film devices can be improved.

Thus, a first aspect of the invention relates to a vapor deposition method for preparing a multilayer thin film structure, the method comprising a vapor source of each component element of a compound intended for the first layer and a compound intended for the second layer. providing a vapor source, wherein the gaseous source comprises at least a source of lithium, a source of oxygen, a source or sources of one or more glass-forming elements, and a source or sources of one or more transition metals. Includes; Heating the substrate to a first temperature; And co-depositing component elements from a vapor source of at least lithium, oxygen and one or more transition metals onto a heated substrate, wherein the component elements form a layer of a crystalline lithium-containing transition metal oxide compound. Reacting on the substrate, wherein the first temperature and the second temperature are substantially in the temperature range of 170 ° C. or less.

This vapor deposition technique not only provides a very simple method for forming crystalline lithium-containing transition metal oxide compounds and amorphous lithium-containing oxide and oxynitride compounds by magnetic capability, but also in a single, non-hazardous manner in either material. It further provides an excellent means for depositing layers of two materials during the process. This is by using substantially the same substrate temperatures to deposit different layers; The temperature range includes suitable deposition conditions for both amorphous and crystalline materials, but small enough to avoid potentially harmful extreme temperatures. In addition, the energy of particles evaporated from gaseous sources is considerably smaller than the particle energies encountered in known techniques such as sputtering, and lower energy particles prevent cluster formation, reduce roughness and produce smooth, undamaged surfaces. To the layers. While obviously a general advantage, this advantage is important when depositing layers of material in devices that can be composed of thin films with thicknesses less than 1 μm. Thus, high quality thin films with precise physical and chemical structures can be produced, and multilayer thin film structures and devices comprising layers of both amorphous and crystalline materials can be readily manufactured.

There are other advantages. Deposition to one of the layers directly in crystalline form reduces processing complexity when compared to known deposition techniques that require post-annealing or ion beams to produce crystallization. For example, the methods of the present invention simplify the known synthesis method described in EP1,305,838 by eliminating the requirement for a secondary source to provide an energized material at a location adjacent to the deposition location.

The layers may be deposited in any order. Thus, in some embodiments, the layer of crystalline lithium-containing transition metal oxide compound is deposited before the layer of amorphous lithium-containing oxide or oxynitride compound, while in other embodiments the amorphous lithium-containing oxide or oxynitride compound The layer of is deposited before the layer of crystalline lithium-containing transition metal oxide compound.

In some embodiments, the temperature range may be substantially 180 ° C to 350 ° C.

Lower temperature ranges may also be accommodated such that the first and second temperatures are substantially 150 ° C. or less, or substantially 100 ° C. or less, or substantially 75 ° C. or less, or substantially 50 ° C. Or less, or substantially in the range 25 ° C. or less, or substantially 10 ° C. or less, or substantially 5 ° C. or less. They effectively provide a quasi-isothermal process, where two or more layers can be deposited at similar temperatures. Alternatively, the process may be isothermal, such that the first temperature and the second temperature are substantially the same. Any of these options greatly improves over known techniques for producing amorphous and crystalline thin films that may require different temperatures by 500 ° C. or more.

As examples, the first temperature may be substantially 350 ° C. and the second temperature may be substantially 225 ° C., or both the first and second temperatures may be substantially 225 ° C. FIG.

The source or sources of one or more transition metals include a manganese source such that the crystalline lithium-containing metal oxide compound is lithium manganese oxide, or the manganese source and nickel source such that the crystalline lithium-containing metal oxide compound is lithium manganese nickel oxide. It may include.

Alternatively, the source or sources of one or more transition metals may be scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, detnium, ruthenium, rhodium And each source of one or more of palladium, silver, cadmium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, palladium, gold and mercury. Of particular interest for depositing materials suitable for cathodes and anodes are cobalt, nickel, manganese, iron, vanadium, molybdenum, titanium, copper and zinc.

The gaseous sources may further comprise a source of nitrogen such that the amorphous compound may be a lithium-containing oxynitride compound.

The source or sources of one or more glass-forming elements may comprise a source of boron and a source of silicon such that the amorphous lithium-containing oxide or oxynitride compound is lithium borosilicate, or one or more glass-forming The source or sources of elements may comprise a source of boron and a source of silicon while the gaseous sources may further comprise a source of nitrogen, such that the amorphous lithium-containing oxide or oxynitride compound is nitrogen-doped lithium borosilicate.

In other embodiments, the amorphous lithium-containing oxide or oxynitride compound may be lithium silicate, lithium oxynitride lithium silicate, lithium borate or oxynitride lithium borate. However, other lithium-containing oxides and oxynitrides are possible, and suitable gaseous sources may be provided accordingly. For example, the source or sources of one or more glass-forming elements may comprise one or more sources of boron, silicon, germanium, aluminum, arsenic and antimony.

In some embodiments, a layer of amorphous lithium-containing oxide or oxynitride compound may be deposited on a layer of crystalline lithium-containing transition metal oxide compound. A layer of crystalline lithium-containing transition metal oxide compound may be deposited to form the cathode of the thin film battery and a layer of amorphous lithium-containing oxide or oxynitride compound may be deposited to form the electrolyte of the thin film battery.

The method may further comprise forming one or more additional layers on the layer of the crystalline lithium-containing transition metal oxide compound and / or the layer of the amorphous lithium-containing oxide or oxynitride compound.

The vapor deposition method can be extended so that at least one additional layer is formed by co-depositing component elements of a compound intended for an additional layer from vapor sources of each component element on the substrate, wherein the component elements are added React on the substrate to form a layer of the compound intended for the layer. The substrate is heated to a third temperature when the third layer is formed, and the first temperature, the second temperature and the third temperature may be substantially in the temperature range of 170 ° C. or less. The first temperature, the second temperature and the third temperature may be substantially the same.

A layer of crystalline lithium-containing transition metal oxide compound may be deposited to form a cathode of a thin film battery, and a layer of amorphous lithium-containing oxide or oxynitride compound may be deposited to form an electrolyte of a thin film battery, one Or further layers may comprise at least the anode of the thin film battery.

Additionally, a layer of crystalline lithium-containing transition metal oxide compound may be deposited to form the cathode of the first thin film battery, and the layer of amorphous lithium-containing oxide or oxynitride compound may form the electrolyte of the first thin film battery. And one or more additional layers may comprise at least the anode of the first thin film battery and the cathode, electrolyte and anode of a second thin film battery formed on the first thin film battery to form a battery stack. .

A second aspect of the present invention uses the vapor deposition method according to the first aspect to deposit a cathode of a battery as a layer of crystalline lithium-containing transition metal oxide compound and to electrolyte of the battery as a layer of amorphous lithium-containing oxide or oxynitride compound. It relates to a method of forming a battery comprising the step of depositing.

A third aspect of the invention relates to a battery comprising a cathode in the form of a crystalline lithium-containing transition metal oxide compound layer and an electrolyte in the form of an amorphous lithium-containing oxide or oxynitride compound layer, wherein the cathode and electrolyte are in accordance with the first aspect. It is deposited using a vapor deposition method.

A fourth aspect of the present invention is directed to an electronic device comprising a battery having a cathode in the form of a crystalline lithium-containing transition metal oxide compound layer and an electrolyte in the form of an amorphous lithium-containing oxide or oxynitride compound layer, the cathode and electrolyte comprising: Deposition is carried out using a vapor deposition method according to one aspect.

A fifth aspect of the invention relates to a sample comprising a crystalline lithium-containing transition metal oxide compound layer and an amorphous lithium-containing oxide or oxynitride compound layer deposited on a substrate using a vapor deposition method according to the first aspect. .

A sixth aspect of the present invention relates to a battery stack comprising a first thin film cell and at least one second thin film cell stacked on the first thin film cell, wherein each thin film cell is a layer of a crystalline lithium-containing transition metal oxide compound. And an electrolyte comprising a cathode and an amorphous lithium-containing oxide or oxynitride compound layer. The crystalline lithium-containing transition metal oxide compound may include lithium manganese oxide or lithium manganese nickel oxide. The amorphous lithium-containing oxide or oxynitride compound may comprise lithium borosilicate or nitrogen-doped lithium borosilicate.

Reference is now made to the accompanying drawings by way of example to show a better understanding of the invention and how the same may be effectively performed.
1 shows a schematic diagram of an example apparatus suitable for implementing a method according to embodiments of the present invention.
2 shows a Raman spectra of samples of metal deposited according to the prior art and a method according to an embodiment of the invention.
3 shows X-ray diffraction measurements of a sample of lithium borosilicate deposited according to an embodiment of the invention.
4 shows the impedance spectrum of a sample of lithium borosilicate deposited according to an embodiment of the invention.
5 shows X-ray diffraction measurements of a sample of nitrogen-doped lithium borosilicate deposited according to an embodiment of the present invention.
6 shows the impedance spectrum of a sample of nitrogen-doped lithium borosilicate deposited according to an embodiment of the present invention.
7 shows X-ray diffraction measurements of samples of lithium manganese oxide deposited according to embodiments of the present invention.
8 shows X-ray diffraction measurements of samples of lithium manganese nickel oxide deposited according to embodiments of the present invention.
9 shows scanning electron microscope images of the surface of samples of lithium manganese oxide deposited according to an embodiment of the present invention when compared to images of surfaces of samples prepared by the prior art method.
10 shows scanning electron microscope images of the surface of samples of lithium manganese nickel oxide deposited according to an embodiment of the present invention when compared to images of surfaces of samples prepared by the prior art method.
11 shows a schematic cross-sectional view of an exemplary thin film battery of conventional structure.
12 shows a graph of voltage beam current vs. time for charge / discharge cycles of a thin film battery having a lithium borosilicate electrolyte and deposited by a method according to an embodiment of the invention.
13 shows a graph of measurements of the discharge capacity of the same battery.
FIG. 14 shows discharge curves measured from samples of lithium manganese oxide in a half cell and deposited according to an embodiment of the present invention.
FIG. 15 shows capacitance measurements taken from samples of lithium manganese oxide in a half cell and deposited in accordance with an embodiment of the present invention, at various discharge rates.
16 shows discharge curves measured from batteries having a lithium manganese oxide cathode and deposited by a method according to an embodiment of the invention.
17 shows a graph of discharge capacities measured over 50 cycles of one battery having a lithium manganese oxide cathode and deposited by a method according to an embodiment of the invention.
18 shows measurements of cyclic voltammetry from a half cell deposited with a lithium manganese nickel oxide cathode and deposited according to an embodiment of the invention.
FIG. 19 shows the discharge curve measured from the cell characterized in FIG. 18.
20 shows charge and discharge curves measured from batteries having a lithium manganese nickel oxide cathode and deposited by a method according to an embodiment of the present invention.
21 (a) and 21 (b) show scanning electron microscopy images of two cell stacks prepared in accordance with embodiments of the present invention, and schematic diagrams of the layers in the stack, respectively.
FIG. 22 shows a plot of X-ray diffraction data measured from the cell stack of FIG. 21.
23 shows a schematic side view of two cell stacks.
24 shows charge and discharge curves measured from batteries having a lithium manganese nickel oxide cathode and deposited by a method according to an embodiment of the invention.

The present invention provides a method for sequentially depositing at least two thin film layers of a thin film structure by vapor deposition. At least two layers comprise lithium-containing compounds, one amorphous compound and one crystalline compound. Each component element of the compound of each layer is provided as a vapor from a separate source and the component element vapor for the first layer is co-deposited on a common heated substrate. The component elements react on the substrate to form the compound of the first layer. The component element vapors for the second layer are then co-deposited on the heated substrate, where the elements react to form the compound of the second layer.

One of the layers includes a crystalline lithium-containing transition metal oxide compound. The other layer comprises an amorphous lithium-containing oxide or oxynitride compound.

In the context of the present disclosure, the term "element" means "element of the periodic table". Thus crystalline lithium-containing transition metal oxide compounds formed in accordance with the present invention comprise component elements comprising lithium (Li), oxygen (O), and one or more transition metals. Other component elements will depend on the particular crystalline compound formed. Amorphous lithium-containing oxides or oxynitride compounds formed in accordance with the invention comprise component elements comprising lithium (Li) and oxygen (O) in the case of oxide compounds, oxygen (O) and nitrogen (N) in the case of oxynitride compounds. Include them. In addition, it comprises one or more glass-forming elements of the component elements.

Other component elements will depend on the particular amorphous compound formed. In all cases, for both crystalline and amorphous compounds, each element of the compound is provided separately in the form of a vapor (if appropriately combined in a mixed vapor or plasma) and each vapor for the first layer Is deposited on a common substrate, followed by the deposition of each vapor for the second layer on the same substrate.

Also in the context of the present disclosure, the term “lithium-containing transition metal oxide compound” means “a compound comprising lithium, oxygen, one or more transition metals, and possibly one or more other elements”. The term "lithium-containing oxide compound" means "a compound comprising lithium, oxygen and one or more other elements", and the term "lithium-containing oxynitride compound" means "lithium, oxygen, nitrogen and one or more thereof." Compound comprising more than the other elements ". A "compound" is a "material or material formed by the combination of two or more elements in fixed proportions by a chemical reaction".

In the context of the present disclosure, the term "crystalline" means "a solid with regular internal arrangements of the properties of atoms, ions or molecules of crystals, ie with long range order within its lattice". In accordance with the methods of the present invention, it has been found that the desired compound may be deposited in intermediate temperatures (described further below) in crystalline form when one or more of the component elements on which the compound is deposited is a transition metal element. In the context of the present disclosure, "transition metal" means any element of the d-block of the periodic table that is groups 3 to 12 on the periodic table, plus the f-block lanthanide element and actinium element series (also "internal transition metals"). Means any element of the " Transition metals of atomic number 72 and below are of particular interest because of their smaller size and weight; These include scandium, titanium, vanadium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, detnetium, ruthenium, rhodium, palladium, silver, cadmium, lutetium and hafnium, in particular electrodes Cobalt, nickel, manganese, iron, vanadium, molybdenum, titanium, copper and zinc for use in materials intended as materials. However, heavier transition metals such as tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, and more are possible.

Further in the context of the present disclosure, the term "amorphous" means "non-crystalline solid", ie a solid that does not have long-range order in its lattice. In accordance with the methods of the present invention, it has been found that the desired compound may be deposited in amorphous form at the substrate temperatures of the present invention if the compound is one or more of the glass forming elements to which it is deposited. Examples of glass-forming elements include boron (B), silicon (Si), germanium (Ge), aluminum (Al), arsenic (As) and antimony (Sb) (Varshneya, AK, Fundamentals of Inorganic Glasses, Academic Press, page 33).

1 shows a schematic diagram of an exemplary apparatus 10 suitable for implementing an embodiment method of the present invention. Deposition is performed in a vacuum system 12 which may be an ultrahigh vacuum system. The substrate 14 of the desired material (depending on the intended purpose of the deposited thin film layers) is mounted in the vacuum system 12 and heated above the room temperature using the heater 16. The temperature is discussed further below. There is also a plurality of vapor sources within the vacuum system, one source for each of the component elements in each of the desired thin film compounds. The first gaseous source 20 includes a source of atomic oxygen, such as an oxygen plasma source. The second gaseous source 22 comprises a source of lithium vapor. These are used for both crystalline and amorphous compounds. For lithium-containing oxides or oxynitrides, the third gaseous source 24 comprises the gaseous source of the glass-forming element, while the fourth gaseous source 26 includes the source of any additional component element of the desired compound. do.

For lithium-containing transition metal oxides, the fifth gaseous source 28 includes a gaseous source of the transition metal element. The sixth vapor source 30 may comprise a source of additional transition metal element, depending on the component elements of the desired transition metal oxide compound. Then, for any one layer, any number of other vapor sources (such as 32, 34, and 36 shown as phantoms) may optionally be included depending on the number of elements included in the compound materials of interest. Can be. For example, the amorphous compound is an oxynitride compound and one of the gaseous sources may be a nitrogen source. Alternatively, where oxygen is provided from the plasma source, nitrogen may be introduced through the plasma source to produce a mixed nitrogen-oxygen plasma.

The nature of each gaseous source will depend on the element it delivers and also the amount of control, or flux, required over the delivery rate. The source may for example be a plasma source, in particular in the case of an oxygen gaseous source. The plasma source delivers plasma-phase oxygen, ie a flux of oxygen atoms, radicals and ions. The source may be, for example, a radio frequency (RF) plasma source. Atomic oxygen is advantageous when depositing compounds containing elements in high oxidation states. Oxygen may alternatively be provided using an ozone source. Plasma sources, such as RF plasma sources, may also be used to deliver nitrogen component vapors when oxynitride compounds are formed or the transition metal oxide comprises nitrogen.

Electron beam evaporators and Knudsen cells (K-cells) are other examples of vapor sources; They are very suitable for materials with low partial pressures. In both cases the material is held in a crucible and heated to produce a flux of material. Knudsen cells use a series of heating filaments around the crucible, while heating in an electron beam evaporator is accomplished by using magnets to direct the beam of high energy electrons to the material.

Other example vapor sources are effusion cells and cracking sources. However, embodiments of the present invention eliminate the need for any cracking, thereby avoiding the complexity inherent in the use of such sources. Further alternative vapor sources will be apparent to those skilled in the art.

During the deposition process, first thin film layer 38 is deposited. If the layers are part of a thin film cell, the first layer 38 may be a layer of crystalline lithium-containing transition metal oxide intended as the cathode of the cell. To achieve this, the controlled flux of each component element in the lithium-containing transition metal oxide is released from its respective vapor source 20, 22, 28 and possibly 30-36 to the heated substrate 14 and thus various The elements are co-deposited. The elements react on the substrate 14 to form a thin film layer 38 of crystalline lithium-containing transition metal oxide.

The second thin film layer 40 is then deposited. In an example of a battery, the second layer can be a layer of amorphous lithium-containing oxide or oxynitride intended as the electrolyte of the cell. To achieve this, the substrate 14 is heated to the same or similar temperature (discussed further below) as used to deposit the first layer 38 and each component element in a lithium-containing oxide or oxynitride The controlled flux of is released from its individual vapor sources 20, 22, 24 and possibly 26 and / or 32-36 to the heated substrate 14 and thus various elements are co-deposited. The elements react on the substrate to form a thin film layer 40 of amorphous lithium-containing oxide or oxynitride on top of the thin film layer 38 of crystalline lithium-containing transition metal oxide.

According to some embodiments, the first and second layers may be deposited in other configurations and orders, and a second crystalline material may be deposited first, such as after an amorphous material. The layers may be on top of one another or side by side. In addition, other thin film layers can be added if desired. In the case of a battery, the anode layer can be deposited on an electrolyte layer as described above. The method described above may be used to deposit a layer or layers in place once the appropriate vapor sources of the required elements are included in the vacuum system 12. Alternatively, previously known deposition techniques can be used. In addition, previously deposited layers may already exist on the substrate 14 before the described crystalline and amorphous layers are deposited from vapor sources.

Depending on the desired configuration of the thin film structure, it may be desirable to use one or more masks to define each layer during deposition. For convenience of processing, the substrate may be allowed to cool after depositing the first layer so that the mask used for the first layer may be exchanged for the mask needed for the second layer. In other embodiments, it may be desirable to maintain the substrate at or within the deposition temperature range while the masks are being changed; This can be faster and more efficient.

According to the invention, the reaction of the component elements to form the compounds of the two layers takes place on the surface of the substrate (or the surface of the previous layer) rather than in the vapor phase before depositing on the substrate. While not wishing to be bound by theory, it is believed that each component element in the vapor impinges and adheres to the surface of the heated substrate, where the atoms of each element are then mobile on the surface and thus form an oxide or oxynitride compound. Can react with each other to form.

Performing the process in vacuum means that the average free path of vapor phase particles moving in vacuum from their respective sources (meaning the distance traveled before colliding with other particles) impinges between the particles before deposition on the substrate. Ensure that this is the way to minimize opportunities. Therefore, the distance from the sources to the substrate is advantageously arranged to be smaller than the average free path in order to increase the chance of particles reaching the substrate without colliding, whereby vapor phase interactions are avoided. The reaction of the component elements is therefore limited to the heated substrate surface and the quality of the thin film compound material is improved.

An advantage of the present invention is that the deposition of the constituents of each compound directly from the elements allows for direct control of the compound composition through the deposition rates of the component elements. The flux of each element can be independently controlled by the proper operation of its respective vapor source so that the chemical composition of the deposited compound can be tailored to the exact requirements as desired. Therefore, direct control of the stoichiometry of the deposited compound is possible by controlling the plus, and consequently the deposition rate of each component element. Conventional deposition techniques, such as sputtering and pulsed laser deposition, can suffer from preferential loss of lighter elements, making it more difficult to control the ratio of elements of the final compound.

In addition, direct deposition from component elements eliminates the need for sputtering targets or precursors, and additional elements can be integrated directly without the requirement to prepare new deposition targets. In addition, deposition of smooth, dense films with undamaged surfaces is possible. Vapor sources such as those exemplified above produce lower energy particles than those produced by sputtering; This lower energy prevents cluster formation and also reduces the surface roughness of the deposited thin film, which is a problem for pulsed laser deposition.

Importantly, the present invention allows for direct deposition of crystalline lithium-rich transition metal oxides. The crystalline feature makes the compounds suitable for use as electrodes, in particular cathodes, in thin film batteries. Under conventional synthesis conditions for large scale thin film samples, a post-deposition annealing step is typically required to crystallize the material, both of which are already pre-deposited materials needed to complicate the process and maintain amorphous Not compatible with The present invention is therefore advantageous to provide a technique for making lithium-based thin film cathodes. Thus, the present invention further allows the formation of amorphous lithium-rich compounds under the same conditions as crystalline lithium-containing transition metal oxides. The amorphous nature makes the compounds suitable for use as electrolytes in thin film batteries. Under both large scale and conventional synthetic conditions for thin film samples, these compounds are known to be crystalline which impair their performance as electrolytes. The present invention is therefore advantageous to provide a technique for forming lithium-based thin film electrolytes. The formation of both crystalline cathode materials and amorphous electrolyte materials under the same conditions and from some of the same element sources provides a very attractive technique for simplifying and improving the fabrication of layered thin film structures such as batteries. The two layers can be deposited sequentially in the same device without the additional process steps required for these components.

An important feature of the invention is the heating of the substrate and the fact that two different layers (crystalline and amorphous) can be deposited directly alternately at the same or similar substrate temperature. This not only simplifies the process for depositing the layers, but also eliminates the problems associated with heating because it does not need to anneal the cathode material to produce crystalline while avoiding heating of the electrolyte material to maintain its amorphous properties. Can be.

Previous work by the inventors (WO 2013/011326, WO 2013/011327) illustrating the synthesis of amorphous phosphor-containing thin film materials by direct deposition of constituent elements on a substrate at room temperature, the technique differs from other materials, It has been suggested that this may be possible for example for lithium-rich glasses. Candidates of interest were lithium borosilicates because of their stability as electrolyte when in amorphous form. However, the use of known methods for phosphates in the component elements of lithium borosilicates does not produce the desired thin film. Under the conditions described in WO 2013/011326 and WO 2013/011327, the component elements do not react on the substrate in the expected manner and the required compound is not produced. Unsatisfactory solutions have been found by replacing atomic oxygen with molecular oxygen; Although this produces the desired amorphous lithium borosilicate at room temperature, the amorphous material will crystallize at the higher temperatures used in other battery manufacturing and processing steps, or crystallize if the battery is used at high temperatures. There is also a risk of cracking the deposited film during later temperature cycling. Samples deposited at elevated temperatures in the presence of molecular oxygen do not form the required phase. In addition, the materials intended as cathodes were produced only as amorphous materials and a separate annealing step at temperatures in the range of 350 ° C. to 750 ° C. was required to produce crystalline cathode materials.

The change of state from amorphous to crystalline at high temperatures is well known and intentionally used in an annealing process for making crystalline materials by heating the amorphous materials. Thus, it is typically understood that high temperatures should be avoided in environments where the material is required to maintain amorphous properties.

As a result, it is surprising and unexpected that samples of amorphous lithium-containing oxides and oxynitrides can be successfully produced by depositing vapor phase component elements directly on a heated substrate. It will be expected that the deposited compound becomes at least partially crystalline due to heating, but according to the invention this is not the case. Although heating of the substrate to about 180 ° C. or more when one or more of the component elements is a glass-forming element has been found to create the conditions necessary for the component elements to react successfully on the substrate surface to form a compound. , Does not cause compound to be crystalline. Stable, good quality amorphous compounds with useful properties are formed.

(LMNO) 박막들은 550℃와 750℃ 사이의 기판 온도들에서 PLD를 사용하여 증착되었지만, 동일한 온도에서 1시간 동안 추후 어닐링이 여전히 요구되었다(Wang et al. Electrochimica Acta 102 (2013) 416-422).When crystalline materials are required and annealing is applied to amorphous materials in accordance with the prior arts, very high temperatures are typically used and an additional distinct step adds complexity to the preparation of the crystalline material. As an alternative, crystallization can sometimes be encountered by heating the substrate during deposition, but again very high temperatures are used. For example, crystalline

(LMNO) thin films were deposited using PLD at substrate temperatures between 550 ° C. and 750 ° C., but annealing was still required for one hour at the same temperature (Wang et al. Electrochimica Acta 102 (2013) 416-422). .

Therefore, it is further surprising that samples of crystalline lithium-containing transition metal oxides can be successfully produced by depositing vapor phase component elements directly on an intermediately heated substrate. "Medium" in this context is defined as the temperature range between about 150 ° C and 350 ° C. These temperatures are much lower than those conventionally used to produce sufficient quality crystallization by annealing, and are also much smaller than the substrate temperatures reported so far used to promote crystallization during deposition by other techniques. Providing component elements comprising lithium, oxygen and one or more transition metals and heating the substrate between about 150 ° C. and 350 ° C. successfully reacts on the substrate surface to form the component elements directly in crystalline form. It was found to create the conditions needed to do so. Stable, good quality crystalline compounds with useful properties are formed.

Thus, we have two unexpected results: production of amorphous materials at temperatures above expected temperatures, and production of crystalline materials at temperatures lower than expected temperatures. While these results are of course important, a particular benefit is that the temperature ranges for the two materials are the same and overlap. Thus, it is attractive to deposit a layer of crystalline material and a layer of amorphous material directly on the same substrate using the same apparatus during the same fabrication procedure, while avoiding the high temperatures that have a detrimental effect on both layered thin film structures and amorphous materials. The arrangement becomes available.

Experimental results

We will now present various experimental results showing the successful manufacture of crystalline and amorphous materials using the described method of direct deposition on a heated substrate from vapor sources of component elements. Examples of various materials alone are examples of layers of materials deposited on battery structures from which measurements showing successful battery operation are obtained to show that desired properties can be achieved for successful use as cathodes and electrolytes. Are provided.

Amorphous materials

lithium Borosilicate

)을 고려하자. 본 발명의 실시예들에 따라, 이 재료는 컴포넌트 엘리먼트들, 리튬, 산소 및 2개의 유리-형성 엘리먼트들, 붕소 및 실리콘으로 형성된다. 리튬 붕규산염의 몇몇 샘플들은 상기 설명된 실시예들과 비슷한 이들 컴포넌트들 엘리먼트들의 기상 증착을 사용하여 다양한 기판 온도들에서 제조되고, 이들의 구조 및 특성들을 결정하기 위하여 라만 분광학을 사용하여 특성화된다. 증착들은 문헌(Guerin, S. and Hayden, B. E., Journal of Combinatorial Chemistry 8, 2006, pages 66-73)에서 이전에 설명되었던 물리적 기상 증착(PVD) 시스템에서 수행된다. 기판 온도를 제외하여, 모든 샘플들은 동일한 조건들하에서 증착되고, 원자 산소의 소스로서 산소 플라즈마 소스를 이용한다. 산화물 재료들, 리튬 규산염 및 리튬 붕산염은 양쪽 실리콘 및 붕소(각각 4+ 및 3+)의 가장 높은 산화 상태들을 요구하고, 그러므로 분자 산소보다 원자 산소의 사용은 재료들(

및

)에서 요구된 바와 같이,

을 2O로 깨뜨리기 위하여 요구된 해리 단계를 제거하고 실리콘 및 붕소를 그들의 가장 높은 산화 상태들로 산화하기 위하여 높은 반응성 종들을 제공한다. 리튬은 크누센 셀 소스로부터 증착되었다. 실리콘 및 붕소 둘 다는 전자 총(E-gun) 소스들로부터 증착되었다.Lithium borosilicate as an exemplary lithium-containing oxide compound that provides a good electrolyte material in amorphous form (

Consider According to embodiments of the present invention, this material is formed of component elements, lithium, oxygen and two glass-forming elements, boron and silicon. Several samples of lithium borosilicates are prepared at various substrate temperatures using vapor deposition of these component elements similar to the embodiments described above and characterized using Raman spectroscopy to determine their structure and properties. Depositions are performed in a physical vapor deposition (PVD) system previously described in Guerin, S. and Hayden, BE, Journal of Combinatorial Chemistry 8, 2006, pages 66-73. Except for the substrate temperature, all samples are deposited under the same conditions and use an oxygen plasma source as the source of atomic oxygen. Oxide materials, lithium silicate and lithium borate require the highest oxidation states of both silicon and boron (4+ and 3+, respectively), and therefore the use of atomic oxygen rather than molecular oxygen is a critical

And

As required by

It removes the dissociation step required to break down to 2O and provides highly reactive species to oxidize silicon and boron to their highest oxidation states. Lithium was deposited from a Knudsen cell source. Both silicon and boron were deposited from E-gun sources.

The initial work was performed without heating (at room temperature, providing a substrate temperature of 29 ° C.) because the amorphous state is the desired form of the material and heating is expected to produce crystallization of the material, which leads to a decrease in ionic conductivity. However, even the deposition carried out using the highest flow of atomic oxygen at room temperature does not result in the material of interest. The lack of the required chemical reaction means that no lithium borosilicate is formed on the substrate.

Surprisingly, it was found that amorphous lithium borosilicate is formed when the substrate is heated during deposition, which results in a material with the required structure and exhibits high ionic conductivity suitable for use as an electrolyte. Then the effect of different substrate temperatures during the deposition was investigated. Measurements of Raman spectra allow monitoring of silicate and borate moieties as a function of deposition temperature, allowing the composition of the thin film to be determined.

Table 1 summarizes the results of these studies in which lithium borosilicate is considered as a Li-B-Si-O ternary system. No B-O or Si-O bonds were observed in samples deposited at temperatures between 29 ° C and 150 ° C, indicating that no lithium borosilicate was formed. It is noted that the materials deposited between 200 ° C. and 275 ° C. exhibit the desired silicate and borate groups (Si-O and B-O). Minimal changes in composition (ratio of various component elements: lithium, oxygen, boron and silicon) were observed at 275 ° C. due to the loss of lithium at this elevated temperature.

Temperature / ℃ Composition B-O Si-O 29 - Not observed Not observed 50-150 No change Not observed Not observed 150 No change Not observed Not observed 200 No change Pyro-borate, ortho-borate, borate ring

디머

체인

시트

Dimmer

chain

Sheet 225 No change Pyro-borate, ortho-borate, borate ring

Dimmer

chain

Sheet 275 Minimum loss of Li (<5 at.%) Pyro-borate, ortho-borate, borate ring

Dimmer

chain

Sheet

The results in Table 1 show that when using an oxygen plasma source, a substrate temperature of 150 ° C. or lower does not produce a lithium borosilicate thin film, while a substrate temperature of 200 ° C. or higher enables the formation of lithium borosilicate. Shows that From these and other measurements, the inventors concluded that heating the substrate to a temperature of about 180 ° C. or higher to form the desired amorphous compound is sufficient for the required chemical reaction to occur on the substrate surface. Regarding the upper temperature limit, it would be undesirable to increase the substrate temperature above about 275 ° C. due to lithium loss without adjusting the sources in this example. However, due to the use of separate sources for the metal elements, the rate of the lithium source can be increased to allow deposition of the material with the correct composition at temperatures higher than 275 ° C. The upper limit for temperature is the temperature at which simultaneous crystallization and reduction in ionic conductivity will occur. Substrate temperatures up to about 350 ° C. are feasible because this will avoid crystallization while still enabling lithium loss compensation by source control. The temperature range of 180 ° C. to 350 ° C. is expected to be applicable to all lithium-containing and glass-forming elements, including oxide and oxynitride compounds, and thus the present invention provides a reliable and simple way to produce amorphous samples of these materials. To provide. However, crystalline lithium-containing metal oxide compounds can be successfully deposited at temperatures in the lower portions of this range (as discussed further below), so higher temperatures can be avoided if desired when manufacturing thin film batteries. Can be.

(±1 at.%)의 라만 스펙트라를 도시한다. 라인(40)은 29

의 스펙트럼을 도시하고 라인(42)은 225

의 스펙트럼을 도시한다. 이들로부터, 실온에서 증착된 재료가 관심 반족들을 포함하지 않는다(어떠한 대역들도 관심 구역에서 관찰되지 않음)을 알 수 있다. 225℃에서 증착된 재료는 관심 있는 붕산염 및 규산염 반족들 둘 다에 할당될 수 있는 대역들을 나타낸다.2 is deposited at room temperature (29 ° C.) and 225 ° C. plotted as strength against wavenumber.

Raman spectra of (± 1 at.%) Are shown. Line 40 is 29

Shows the spectrum of the line 42 at 225

Shows the spectrum of. From these, it can be seen that the material deposited at room temperature does not contain the reaction groups of interest (no bands are observed in the region of interest). The material deposited at 225 ° C. shows bands that can be allocated to both borate and silicate groups of interest.

의 전도율 값을 가진다. 이런 레벨의 전도율의 관찰은 양쪽 관심 재료, 리튬 붕규산염이 상승된 온도에서 생성되었고 결정화가 증착 동안 재료의 가열로 인해 발생되지 않았다는 것을 확인시킨다. 재료가 결정화되었다면 이온 전도율은 몇 배만큼 감소될 것이다. 이런 재료의 X-선 회절은 결정화가 발생하지 않았다는 것을 확인시킨다.In addition, impedance measurements were performed on materials deposited at 29 ° C and 225 ° C. Since the material does not show any ionic conductivity, it was not possible to determine the ionic conductivity of the materials deposited at 29 ° C. This is consistent with the negligible formation of silicate and borate families. In contrast, the material deposited at 225 ° C. exhibited a definite ion conduction process,

It has a conductivity value of. Observation of this level of conductivity confirms that both materials of interest, lithium borosilicate, were produced at elevated temperatures and that no crystallization occurred due to heating of the material during deposition. If the material is crystallized the ionic conductivity will be reduced by several times. X-ray diffraction of this material confirms that no crystallization has occurred.

Thus, as an unexpected result, it is obtained that an amorphous thin film of a lithium-containing oxide compound can be formed on a heated substrate.

Amorphous lithium Borosilicate  Further characterization

As described, lithium borosilicate thin films were prepared at elevated temperatures, including 225 ° C. In contrast to the expectations based on the understanding that heating causes crystallization, these thin films were observed to be amorphous.

기판의 재료들에 인한다. 도 3은 Pt 및

("!" 및 "*"으로 각각 표시됨)에 대한 기준 패턴들을 포함하고, 이는 관찰된 피크들이 박막보다 오히려 기판으로부터 발생하는 것을 나타낸다. 리튬 붕규산염으로 인한 임의의 피크들의 부재는, 증착된 재료가 비정질인 것을 나타낸다.3 shows the results of X-ray diffraction measurements performed to investigate the crystal structure of lithium borosilicate. As can be seen, the X-ray diffraction plot does not show any clear peaks resulting from lithium borosilicate. Rather, the peaks shown support the lithium borosilicate thin film.

Due to the materials of the substrate. 3 is Pt and

(Represented by "!" And "*", respectively), indicating that the observed peaks occur from the substrate rather than the thin film. The absence of any peaks due to lithium borosilicate indicates that the deposited material is amorphous.

To further test the lithium borosilicate samples, impedance measurements were performed at room temperature to determine ionic conductivity.

이다. 이들 측정들로부터, 이온 전도율은

인 것으로 결정되었다. 이것은 재료가 리튬 이온 배터리에서 전해질로서 사용하기에 적당하게 하고, 현재 가장 일반적으로 사용되는 박막 전해질의 이온 전도율, LIPON(

)과 비슷하다.4 shows the results of impedance measurements as the impedance spectrum of a sample of lithium borosilicate deposited at a substrate temperature of 225 ° C. FIG. The chemical composition of the thin film

to be. From these measurements, the ionic conductivity is

Was determined to be. This makes the material suitable for use as an electrolyte in lithium ion batteries, and the ionic conductivity, LIPON (

Similar to).

Nitrogen-doped lithium Borosilicate

The above-described preparation of lithium borosilicate has been modified to show its flexibility and applicability in the production of other lithium-containing oxide and oxynitride compounds. Nitrogen-doped lithium borosilicate was produced by introducing nitrogen into the gas supplied to the oxygen plasma source to deliver the mixed oxygen-nitrogen flux. Lithium, boron and silicon were provided as previously described and the temperature of the substrate was 225 ° C. Various substrate temperatures similar to those shown for undoped lithium borosilicate are also applicable to nitrogen-doped materials, ie about 180 ° C., which is likely to produce rainwater material in a simple manner without the need to control lithium loss, for example. To about 350 ° C, a narrower range of about 180 ° C to about 275 ° C is applicable.

5 shows the measured X-ray diffraction plot of the resulting nitrogen-doped lithium borosilicate thin film. Peaks on the graph (denoted by "!") Are due to the platinum of the AlOPt substrate. The absence of other peaks indicates that the sample is amorphous and free of crystalline structure.

의 컴포지션을 가진 질소-도핑 리튬 붕규산염 박막의 임피던스 스펙트럼을 도시한다. 이런 측정으로부터, 이온 전도율은

인 것으로 결정된다. 이들 결과들은 이 프로세스의 융통성을 나타내고, 이는 쉽게 질소에 비정질 리튬 붕규산염의 성공적인 도핑을 가능하게 한다. 도핑은

로부터

로의 화합물의 이온 전도율의 명확한 개선을 나타낸다. 이것은 전해질 재료 LiPON에 대해 이전에 도시된 재료의 성능을 상당히 넘게 개선하고 그러므로 고체 상태 배터리의 성능을 개선하기 위한 간단하고 효과적인 수단을 제공한다.6

Shows the impedance spectrum of a nitrogen-doped lithium borosilicate thin film with a composition of. From these measurements, the ionic conductivity

Is determined to be. These results show the flexibility of this process, which allows for the successful doping of amorphous lithium borosilicate into nitrogen easily. Doping

from

A clear improvement in the ionic conductivity of the compound into the furnace. This significantly improves the performance of the material previously shown for the electrolyte material LiPON and therefore provides a simple and effective means for improving the performance of solid state batteries.

Crystalline materials

As examples, crystalline lithium manganese oxide and crystalline lithium manganese nickel oxide thin films were prepared by direct deposition from elements on heated substrates as described above.

(10 nm) 및 백금(100 nm)(AlOPt, from Mir Enterprises)로 코팅된 사파이어 기판들상에 증착되었다.Unless otherwise stated, the depositions were Guerin, S; Hayden, BE, J. Comb. The arrangements described in Chem., 2006, 8, 66 and WO 2005/035820 were performed in ultra-high vacuum (UHV) systems. The curtains

(10 nm) and platinum (100 nm) (AlOPt, from Mir Enterprises) were deposited on sapphire substrates.

Lithium manganese oxide and lithium manganese nickel oxide (LMO and LMNO, respectively) intended as cathode were synthesized from lithium, manganese, nickel and oxygen sources. Manganese and lithium were deposited from Knudsen cells. Nickel was deposited from an electron beam evaporator and oxygen was provided by a plasma atomic source.

Various samples of LMO were deposited at substrate temperatures between 25 ° C and 450 ° C. By modifying the substrate temperature used, the threshold for crystallization is determined, and the crystallization of the resulting material is enhanced as the temperature is raised.

(00-035-0782)의 111 반사와 일치하는 ca. 18.6°에서 작은 피크를 나타낸다는 사실로부터 알 수 있다. 200℃ 미만의 온도들에서 LMO의 박막들의 증착이 X-선 비정질 재료들을 초래하는 종래 기술이 주어지는 경우 단지 150℃의 기판 온도에서 X-선 회절에 의한 결정화의 관찰은 놀랍다. 기판 온도를 250℃까지 추가로 증가시키는 것(라인 48)은 111 반사의 강화된 피크 강도에 의해 나타난 바와 같이 결정화를 추가로 강화하는 것이 주의된다. 350℃에서 증착된 LMO(라인 50)는 그 각도에서 피크 강도의 추가 강화를 나타낸다.7 shows the results of X-ray diffraction measurements of samples of LMO deposited at different temperatures. Line 44 represents the LMO deposited at room temperature (25 ° C.) which does not show clear peaks in the diffraction pattern. This is consistent with the amorphous material as expected for deposition at room temperature. Increasing the substrate temperature to 150 ° C. (line 46) causes crystallization to occur, which means that the diffraction pattern recorded for this sample

(00-035-0782), ca. It can be seen from the fact that it shows a small peak at 18.6 °. Observations of crystallization by X-ray diffraction at substrate temperatures of only 150 ° C. are surprising given the prior art that the deposition of thin films of LMO at temperatures below 200 ° C. results in X-ray amorphous materials. It is noted that further increasing the substrate temperature to 250 ° C. (line 48) further enhances crystallization as indicated by the enhanced peak intensity of the 111 reflection. LMO deposited at 350 ° C. (line 50) shows further enhancement of peak intensity at that angle.

Determining the full width at half maximum (FWHM) for these peaks provides a further understanding of the improved crystallization. As the microcrystals grow, the FWHM decreases due to larger microcrystals that provide enhanced alignment. LMO deposited at 150 ° C. shows an FWHM of 0.882 °. This can be translated by the Scherrer equation to a suitable microcrystalline size, in this case approximately 9 nm. Increasing the deposition temperature to 250 ° C. results in a decrease in FWHM to 0.583 °, and accompanying increases the microcrystalline size to 14 nm. Further increase to a temperature of 350 ° C. results in an FWHM of 0.471 ° and a microcrystalline size of 17 nm.

Thus, good quality constituent crystalline material is achieved at these intermediate substrate temperatures. This represents a significant improvement over known techniques by eliminating the need for post-annealing and by reducing the manufacturing temperature when compared to what is needed for annealing.

Lithium manganese nickel oxide (LMNO) samples were prepared under various conditions using the techniques detailed previously. Again, the crystalline material was successfully deposited directly only at intermediate substrate temperatures. By modifying the substrate temperature used, the crystallization of the resulting material can be enhanced.

(04-015-5905)의 111 반사와 일치하는 ca.18.6°에서 작은 피크를 나타낸다. 기판 온도를 추가로 250℃로 증가시키는 것(라인 56)은 111 반사의 더 큰 피크 강도에 의해 나타난 바와 같이 결정화를 추가로 강화시키는 것이 주의된다. 350℃에서 증착된 재료(라인 58)는 그 각도에서 피크 강도의 추가 강화를 나타내고, 450℃에서 증착된 LMNP(라인 60)는 그 각도에서 피크 강도의 부가적인 강화를 나타낸다.8 shows the results of X-ray diffraction measurements of samples of LMNO deposited at different temperatures. The material deposited at room temperature (25 ° C.) shown by line 52 does not show any clear peaks in diffraction patterns consistent with the amorphous material expected at this temperature. Increasing the temperature to 150 ° C. (line 54) enhances crystallization,

(04-015-5905) shows a small peak at ca. 18.6 ° consistent with the 111 reflection. It is noted that increasing the substrate temperature further to 250 ° C. (line 56) further enhances crystallization as indicated by the greater peak intensity of the 111 reflection. Material deposited at 350 ° C. (line 58) shows further enhancement of peak intensity at that angle, and LMNP (line 60) deposited at 450 ° C. shows additional enhancement of peak intensity at that angle.

Determining the full width at half maximum (FWHM) for these peaks provides a further understanding of the improved crystallization. As the microcrystals grow, the FWHM decreases due to larger microcrystals that provide enhanced alignment. LMNO deposited at 150 ° C. shows an FWHM of 0.841 °. This can be translated by the Scherrer equation to a suitable microcrystalline size, in this case approximately 10 nm. Increasing the deposition temperature to 250 ° C. results in a slight decrease in FWHM to 0.805 °, which results in a microcrystalline size of approximately 10 nm. Further increase to a temperature of 350 ° C. results in a FWHM of 0.511 ° and a microcrystalline size of 10 nm. Depositions performed at 450 ° C. resulted in FWHM of 0.447 ° and microcrystalline size of 18 nm.

Thus, for LMO, good quality constituent crystalline LMNO can be achieved with these intermediate temperature substrates. Indeed, X-ray diffraction measurements of LMNO clearly show that it is possible to deposit crystalline LMNO at significantly lower intermediate temperatures than those previously shown without the need for any post annealing, or application energy for secondary sources such as ion sources. Indicates. As a comparison, it has previously been shown that the annealing processes required to produce crystalline LMNO with sol-gel samples require three annealing at 750 ° C. and further annealing at 800 ° C. (Zhong, Q., et al., J. Electrochem. Soc., (1997), 144 (1), 205-213).

Crystalline LMO  And LMNO's  Surface Characterization

The surface morphology of the LMO and LMNO deposited in accordance with embodiments of the present invention was compared with those deposited by alternative methods to determine any improvements.

9 (a) -9 (e) show some of the results in the form of scanning electron microscope (SEM) images at 30 K X magnification. 9 (e) and 9 (d) show LMO thin films deposited according to the present invention at substrate temperatures of 225 ° C. and 350 ° C., respectively, while FIGS. 4 (a), 4 (b) and 4 (c) shows LMO films deposited using RF sputtering at substrate temperatures of 200 ° C., 300 ° C. and 400 ° C., respectively (Jayanth et al. Appl Nanosci (2012) 2: 401-407). It is noted that the LMO deposited according to the invention at both 225 ° C and 350 ° C exhibits significantly reduced roughness when compared to that deposited by RF sputtering at 200 ° C and 300 ° C. Only a very small number of features of approximately 100 nm diameter were observed on the LMO film deposited according to the invention at 350 ° C. and a smaller number was observed on the film deposited at 225 ° C. These samples are considerably softer than films deposited by sputtering; For example, a film deposited at 300 ° C. can be observed to have features with diameters on the order of 1 μm. Features observed in sputtered films are generally larger in size than those observed in films deposited according to embodiments of the present invention, which will make a significant difference when these thin films are assembled into devices. For example, such enhanced film quality is important when depositing multiple thin layers of films on top of each other. If LMO is used as a cathode in a solid state battery, a moderately thin layer of solid electrolyte is deposited on the LMO to prevent direct contact between the underlying anode and the LMO caused by surface protrusions extending into and through the electrolyte. It will be necessary to deposit. The increased softness of the LMO layer as can be achieved by the use of the present invention results in the use of thinner layers of electrolyte, which results in the production of more efficient solid state batteries and cheaper and more efficient batteries.

10 (a) and 10 (b) show compared SEM images of LMNO samples. 10 (a) shows LMNO deposited according to the invention at 350 ° C., FIG. 10 (b) shows magnetic sputtering with post annealing at 700 ° C. (top image) and 750 ° C. (bottom image) in air. LMNO deposited by (Baggetto et al., J. Power Sources, (2012), 211, 108-118). As can be seen from these images, the samples prepared according to the present invention exhibit significantly smoother and dense film surfaces than prior art film surfaces deposited by sputtering with post-annealing.

Description of functional batteries

The amorphous nature of undoped and doped lithium borosilicates with high ionic conductivity indicates that these thin films are very suitable for use as electrolyte in thin film batteries. Similarly, crystalline LMO and LMNO are very suitable for use as cathodes. Therefore, various thin film half cells and batteries are generated using the vapor deposition process described and characterized to represent the overall functionality.

11 shows a schematic cross-sectional view of an exemplary lithium ion thin film battery or cell 70 of a conventional structure. Such batteries typically comprise a series of layers formed by one or more deposition or other fabrication processes. The vapor deposition method of the present invention is advantageous for this because good quality electrode and electrolyte materials can be deposited directly on the same or similar temperature substrate. In the exemplary battery 70, the substrate 72 supports various layers. In order starting from the substrate they are the cathode current collector 74, the cathode 76, the electrolyte 78, the anode 80 and the anode current collector 82. Protective encapsulation layer 84 is formed over the layers. In other examples, the layers may be arranged in the reverse order except for the encapsulation layer, which will always be the final layer if included.

Experimental Battery Results: Lithium Borosilicate  Electrolyte and Lithium Manganese Oxide Cathode

(10nm)로 코팅된 사파이어 기판들 상에서 수행되었다(Mir Enterprises로부터의 AlOPt 기판). 캐소드에 대해, 리튬 망간 산화물(LMO)의 박막은 리튬, 망간 및 산소 소스들로부터 합성되었다. 망간 및 리튬은 크누센 셀들로부터 증착되는 반면 산소는 플라즈마 원자 소스에 의해 제공되었다. 증착은 7620 초 동안 수행되었고, 300 nm의 균일한 두께의 박막을 제공한다. 기판의 온도는 본 발명의 실시예들에 따라 결정질 재료를 제공하기 위하여 350℃에서 유지된다. 그러나, 이것은 단지 예시이고 LMO 캐소드 층은 상기 논의된 바와 같이 다양한 컴포넌트들에 대한 대안 소스들, 및 다른 온도들 및 다른 시간들 동안 증착될 수 있다. LMO 증착의 종료시 리튬 및 망간 소스 셔터(shutter)들은 이들 엘리먼트들의 플럭스를 차단하기 위하여 폐쇄되었다. 기판은 360 초의 기간에 걸쳐 350℃로부터 225℃로 냉각되고, 그 시간 동안 원자 산소의 플럭스에 노출이 계속된다.Samples containing the cathode, electrolyte and anode layers were prepared in the experiments to represent the working cells. In a first example, the deposition of three constituent films (cathode, electrolyte and anode) of a thin film battery is performed in an ultrahigh vacuum system.

(10 nm) coated on sapphire substrates (AlOPt substrate from Mir Enterprises). For the cathode, a thin film of lithium manganese oxide (LMO) was synthesized from lithium, manganese and oxygen sources. Manganese and lithium were deposited from Knudsen cells while oxygen was provided by a plasma atomic source. The deposition was performed for 7620 seconds, giving a thin film of uniform thickness of 300 nm. The temperature of the substrate is maintained at 350 ° C. to provide a crystalline material in accordance with embodiments of the present invention. However, this is merely an example and the LMO cathode layer may be deposited for alternative sources for various components and other temperatures and other times as discussed above. At the end of the LMO deposition the lithium and manganese source shutters were closed to block the flux of these elements. The substrate is cooled from 350 ° C. to 225 ° C. over a period of 360 seconds, during which time exposure to the flux of atomic oxygen continues.

The electrolyte was a thin film of lithium borosilicate also deposited in accordance with embodiments of the present invention. It was synthesized using lithium, boron, silicon and oxygen sources. For the cathode, lithium was deposited from the Knudsen cell and the plasma source provided atomic oxygen. Boron and silicon were deposited from electron beam depositors. The substrate was held at 225 ° C. during the deposition of the electrolyte, which continued for 14400 seconds to provide a 800 nm thick thin film. However, this process is merely illustrative and the amorphous lithium borosilicate electrolyte layer may be deposited for alternative sources for various component elements, and for other temperatures and other times, as discussed above.

박막 배터리가 생성되었다.Next, a physical mask was placed on the front of the sample to define 1 × 1 mm discrete batteries without removing the sample from the vacuum. This takes less than 600 seconds. The thin oxide anode was then deposited using a Knudsen cell tin source and an atomic oxygen plasma source, over a course of 180 seconds. The thickness of the resulting anode layer is estimated to be 9.6 nm (based on calibration measurements). Finally, the 100 nm layer of nickel was added as the top current collector using an electron beam evaporator and a second mask with 1.5 × 15 nm apertures, again the sample was in vacuum. therefore,

Thin film batteries were produced.

X-ray diffraction measurements confirmed that, as expected in accordance with the present invention, the LMO cathode deposited at 350 ° C. was crystalline and the lithium borosilicate electrolyte deposited at 225 ° C. was amorphous.

Although each of the cathode, electrolyte and anode layers in this example is fabricated using vapor deposition of component elements on a heated substrate, it is noted that the anode layer is made by any convenient and suitable thin film fabrication process as desired. Other anode materials can also be used and can be manufactured as desired. The layers can also be deposited in a different order, such as first an anode, then an electrolyte, and then a cathode.

To test the operation of the cell, the contact was made through two pin probes in a glove box. Charge and discharge measurements were performed using a constant current-constant voltage (CC / CV) instrument.

에 대응함). 이것은 애노드 제한 시스템에 기초하여 이론적 용량의 83%에 대응한다. 20 사이클들 후 용량은 애노드 제한 시스템에 기초하여 이론적 용량의 33%에 대응하는 0.015 mA h(

)로 강하하는 것을 관찰되었다. 용량은 이 레벨에서 안정되는 것으로 주의되었고 추가 29 사이클들 다음 용량은 0.016 mA h인 것으로 관찰되었다.12 and 13 show the results of these measurements. 8 shows a plot of voltage and current versus time during first charge / discharge cycles. Curve 86 shows the cell potential and curve 88 shows the current. 10 shows measurements of discharge capacity over first 50 cycles. The cell showed a maximum of capacity over the first 10 cycles and the capacity stabilized after 20 cycles. The maximum discharge capacity of 0.077 mA h was observed in cycle 2 (

Corresponding to). This corresponds to 83% of theoretical capacity based on the anode limiting system. After 20 cycles, the capacity is 0.015 mA h (corresponding to 33% of theoretical capacity based on the anode limiting system)

Descent). The dose was noted to be stable at this level and the dose following an additional 29 cycles was observed to be 0.016 mA h.

It is believed that this is the first reported demonstration of a fully functioning thin film battery in which the cathode, electrolyte and anode layers are all deposited as thin film layers directly from the component elements.

Experimental Battery Results: Deposited at 225 ° C LMO Cathode

의 주기적 볼타메트리 및 정전류/정전압(CC/CV) 측정들은, 본 발명의 실시예들에 따라 생성된 막들이 전기화학적으로 액티브하다는 것을 나타냈고, 용량들은 문헌에 설명된 것들과 유사하다.Deposited at a substrate temperature of 225 ° C. and used in either liquid electrolyte half cells or solid state full cells

Periodic voltametry and constant current / constant voltage (CC / CV) measurements of showed that the films produced according to embodiments of the present invention are electrochemically active and the capacities are similar to those described in the literature.

To further test the capacity of thin films deposited according to the present invention to function in thin film cells, the half-cell of lithium manganese oxide (LMO) was used at a suitable rate from separate gaseous sources, using a substrate temperature of 225 ° C. It was produced by co-depositing lithium, manganese and oxygen. The conditions used were determined by depositing test samples, and the composition determined using laser ablation inductively coupled mass spectrometry (ICPMS) and rates of lithium and manganese sources, accordingly to obtain optimal conditions for the deposition of the desired composition. Changed. An LMO with a thickness of 300 nm was deposited on the platinum pad over an area of 2.25 mm ² and assembled into lithium metal as a half cell and counter electrode with 1 M LIPF ₆ = 1: 1 of EC: DMC as electrolyte.

에서 0.1 내지 25 mV/s(0.2 내지 45 C) 범위의 다양한 레이트들에서 LMO 박막들의 방전 곡선들을 도시한다.Figure 14 shows the potential window between 4.3 and 3.0 V

The discharge curves of the LMO thin films at various rates in the range of 0.1 to 25 mV / s (0.2 to 45 C).

에서 0.1 내지 25 mV/s(0.2 내지 45 C)의 다양한 레이트들에서 방전되는 LMO 박막들의 측정된 용량들을 도시한다.Figure 15 shows the potential window between 5.0 and 3.0 V

Shows measured capacities of LMO thin films discharged at various rates of 0.1 to 25 mV / s (0.2 to 45 C).

또는

의 방전 용량을 가지는 것을 관찰한다. 충전 및 방전 시간들은 C-레이트들로서 표현되고 여기서 1C-레이트는 1 시간의 완전한 충전/방전에 대응하고; 'n' C-레이트는 1/n 시간들에서 셀을 충전/방전시킬 것이다. 보통, 배터리들은 상당히 느린 레이트들을 사용하여 충전 및 방전되고 레이트가 증가함에 따라 허용 가능한 용량이 감소한다. 실제로, "대부분의 상업적 셀들은 10 C 만큼 느리게 시작하는 레이트들에서 충전될 때 저장된 에너지의 몇 퍼센트만을 사용한다"(Braun, P.V., Current Opinion in Solid State Materials Science, 16, 4 (2012), 186-198). 이들 결과들은 다른 방법들을 사용하여 유사한 기판 온도들에서 증착되는 LMMO에 비해 개선이다. 200℃에서 RF- 스퍼터링에 의해 증착된 LMO 박막들은

의 방전 용량을 가지는 것으로 도시되었고(Jayanth et al. Appl Nanosci (2012) 2:401-407) 200℃에서 PLD에 의해 증착된 LMO는

의 방전 용량을 가지는 것을 도시되었다(Tang et al. J. Solid State Chemistry 179 (2006) 3831-3838). 실험은 0.1과 150 mV/s 사이의 스위프(sweep) 레이트들(0.2와 270 C 사이의 C 레이트들과 동일함)을 사용하여 3 및 5 V의 전위 제한들 사이의 주기적 볼타메트리를 사용하여 사이클링함으로써 증착된 LMO의 레이트 용량을 연구하기 위하여 수행되었다. 결과들은, 4.3과 3.0 V 사이의 전위 윈도우 대

에서 0.1 내지 25 mV/s(0.2 내지 45 C) 범위의 다양한 레이트들에서

박막들에 대한 스위프 레이트의 함수로서 용량들의 요약으로서 표 2에 도시된다.From these measurements, we find that the capacity of the LMO material is at a charge and discharge rate of 1 C.

or

It is observed to have a discharge capacity of. Charge and discharge times are expressed as C-rates, where 1C-rate corresponds to 1 hour of full charge / discharge; 'n' C-rate will charge / discharge the cell at 1 / n times. Usually, batteries are charged and discharged using significantly slower rates and the allowable capacity decreases as the rate increases. Indeed, "most commercial cells use only a few percent of the stored energy when charged at rates starting as slow as 10 C" (Braun, PV, Current Opinion in Solid State Materials Science, 16, 4 (2012), 186 -198). These results are an improvement over LMMO deposited at similar substrate temperatures using other methods. LMO thin films deposited by RF-sputtering at 200 ° C

(Jayanth et al. Appl Nanosci (2012) 2: 401-407) and LMO deposited by PLD at 200 ° C.

It has been shown to have a discharge capacity of (Tang et al. J. Solid State Chemistry 179 (2006) 3831-3838). The experiment uses periodic voltammetry between potential limits of 3 and 5 V using sweep rates between 0.1 and 150 mV / s (equivalent to C rates between 0.2 and 270 C). This was done to study the rate capacity of the deposited LMO by cycling. The results show the potential window between 4.3 and 3.0 V.

At various rates ranging from 0.1 to 25 mV / s (0.2 to 45 C)

It is shown in Table 2 as a summary of the capacities as a function of the sweep rate for thin films.

Rate / mV / s (C) Capacity / mA / h / g Percentage capacity (comp. 0.2C) 1 (1.8 C) 57.7 85 0.1 (0.2 C) 67.5 100 0.5 (1 C) 61.8 92 2 (3.6 C) 48.9 72 5 (9 C) 36.7 54 10 (18 C) 28.7 43 1 (1.8 C) 56.1 83 25 (45 C) 20.4 30 50 (90 C) 17.3 26 100 (180 C) 13.8 20 150 (270 C) 12.0 18

인 것으로 관찰되었다. 추가 15 사이클들 다음, 45 C까지의 레이트들에서 PVD LMO의 용량은 단지

까지 강하(3.2% 손실)하는 것으로 관찰되었다. 높은 레이트들(270 C)에서 사이클링될 때, PVD에 의해 증착된 LMO는 용량의 단지 중간의 손실들을 나타내고; 표 2를 보라. 이들 손실들은 다른 수단에 의해 증착된 LMO에서 관찰된 것들보다 상당히 작다. 예컨대, Chen 등(Thin Solid Films 544 (2013) 182-185)은 높은 레이트 성능 LMO를 주장한다. 이 경우 LMO는 45 C에서 사이클링될 때 기껏 자신의 초기 용량의 단지 22%(0.2 C에서)를 나타낸다. 직접 비교시, 본 발명에 의해 증착된 LMO는 자신의 용량의 30%를 유지한다. 높은 레이트들에서 LMO의 용량을 액세스할 수 있는 것은, 재료가 높은 파워의 짧은 버스트(burst)들을 요구하는 애플리케이션들에 유용하다는 것을 의미한다.Thus, the LMO deposited by the methods according to embodiments of the present invention exhibits excellent cycle capability and only moderate loss when cycled at increased rates, as shown in FIG. 15, ignored over 35 cycles. Indicates a possible capacity loss. The average capacity over cycles 1-19 is

Was observed. After an additional 15 cycles, the capacity of the PVD LMO at rates up to 45 C is only

It was observed to fall (3.2% loss). When cycled at high rates 270 C, the LMO deposited by PVD exhibits only moderate losses of capacity; See Table 2. These losses are considerably smaller than those observed in LMO deposited by other means. For example, Chen et al. (Thin Solid Films 544 (2013) 182-185) insist on high rate performance LMO. In this case, LMO represents only 22% (at 0.2 C) of its initial dose when cycled at 45 C. In direct comparison, the LMO deposited by the present invention maintains 30% of its capacity. Being able to access the capacity of the LMO at high rates means that the material is useful for applications that require short bursts of high power.

These results from the half-cell indicate that a battery comprising an LMO cathode on which an amorphous electrolyte layer according to embodiments of the present invention is deposited will provide excellent performance.

에서 1 내지 45 C 범위의 다양한 레이트들에서 방전되었다. 셀들은 1mm²의 영역을 가졌고 초고도 진공에서 물리적 기상 증착에 의해 완전히 증착되었고, 이때 LMO 캐소드들 및 리튬 붕규산염 전해질들은 본 발명의 실시예에 따라 증착된다. 300 nm의 LMO 캐소드는 10 nm의

및 100 nm의 Pt로 코팅된 사파이어 기판상에 리튬, 망간 및 산소 소스들로부터 직접 증착된다. 기판의 온도는 캐소드 증착에 걸쳐 225℃에서 유지되고, 이는 적소의 열전쌍에 의해 모니터링된다. 리튬 붕규산염을 포함하는 고체 상태 전해질은 800 nm의 두께를 제공하기 위하여 225℃에서 리튬, 붕소, 실리콘 및 산소 소스들로부터 직접 증착된다.

애노드는 10 nm의 두께를 제공하기 위하여 225℃에서 일단 다시 주석 및 산소로부터 직접 증착되었다. 이들 증착들은 동일한 진공 챔버 내에서 번갈아 수행되었다. 니켈 전류 컬렉터는

층의 완성 다음, 그리고 샘플이 실온(17℃로 냉각된 후) PVD에 의해 증착되었다.FIG. 16 shows the discharge curves from CC / CV experiments on solid state cells comprising an LMO cathode deposited at a substrate temperature of 225 ° C. in accordance with the present invention. The cells have a potential window between 4.0 and 2.5 V

At various rates ranging from 1 to 45 C. The cells had an area of 1 mm ² and were fully deposited by physical vapor deposition in ultrahigh vacuum, where LMO cathodes and lithium borosilicate electrolytes were deposited according to an embodiment of the present invention. 300 nm LMO cathode is 10 nm

And deposited directly from lithium, manganese and oxygen sources on a sapphire substrate coated with 100 nm of Pt. The temperature of the substrate is maintained at 225 ° C. throughout the cathode deposition, which is monitored by the thermocouple in place. Solid state electrolytes comprising lithium borosilicate are deposited directly from lithium, boron, silicon and oxygen sources at 225 ° C. to provide a thickness of 800 nm.

The anode was deposited directly from tin and oxygen once again at 225 ° C. to provide a thickness of 10 nm. These depositions were performed alternately in the same vacuum chamber. Nickel current collector

Following completion of the layer, the sample was deposited by PVD at room temperature (after cooling to 17 ° C.).

Thus, all three cathode, electrolyte and anode layers were deposited directly from the vapor sources of their component elements at the same substrate temperature for the deposition of each layer, which truly represents isothermal battery fabrication. This is very advantageous over conventional battery manufacturing, which uses different deposition techniques at different temperatures for different layers and typically requires other processing steps such as annealing.

와 동일한

이고; 이는 LMO 및

를 가지며 액체 전해질을 사용하는 셀의 이전 설명과 비교될 때 상당한 개선을 도시하고, 여기서 밸런싱된 셀에 대해 10

의 방전 용량들이 보고되었다(Park, Y. J. et al., J. Power Sources, 88, (2000), 250-254). 결과들은, 셀이 높은 레이트들에서 기능할 수 있다는 것을 나타내고, 45 C까지의 레이트들이 보여진다. 높은 레이트들은 파워의 짧은 버스트들이 요구되는 높은 파워 애플리케이션들에 대해 필요하다.As can be seen in FIG. 16, the initial capacity of these cells when cycled at 1 C is

Same as

ego; This is LMO and

And a significant improvement when compared to the previous description of a cell using a liquid electrolyte, wherein 10 for a balanced cell

Discharge capacities have been reported (Park, YJ et al., J. Power Sources, 88, (2000), 250-254). The results indicate that the cell can function at high rates and rates up to 45 C are shown. High rates are needed for high power applications where short bursts of power are required.

17 shows further experimental results for these cells in the form of a plot of discharge capacity over the course of 50 cycles of one cell. The cell was charged and discharged at a rate of 1 C between 4.0 and 2.5 V. Initial capacity loss was observed during the first 20 cycles, but then capacity retention is quite good and indicates that a rechargeable cell is produced.

Experimental Battery Results: Deposited at 350 ° C LMNO Cathode

In the same manner as LMO, LMNO deposited according to embodiments of the present invention at a substrate temperature of 350 ° C. has been shown to be electrochemically active.

및 카운터 전극으로서 리튬 금속을 사용하여 완성되었다.Half cells of lithium manganese nickel oxide (LMNO) were produced by using the method according to an embodiment of the present invention to co-deposit lithium, manganese, nickel and oxygen at an appropriate rate at a substrate temperature of 350 ° C. An electrochemical array consisting of silicon / silicon nitride substrates and platinum pads was used as the substrate in this case. Half-cell is an electrolyte of EC: DMC = 1: 1

And lithium metal as a counter electrode.

의 스위프 레이트로 수행되었고, 이는 1.8 C의 동일한 충전 레이트를 제공한다. 피크들은 4.1 V 및 4.7 V에서 충전 동안 명확하게 보여질 수 있고, 이는 막들에

및

양쪽의 존재를 가리킨다. 이로부터, 컴포지션

(여기서

는 0과 0.5 사이임)을 가지는 산소 결함 LMNO가 생성되었다는 것이 추정되었다.18 shows the results of the periodic voltametry performed on this cell over a first cycle. These measurements are between 1 and 3 V

Was performed at a sweep rate of, which gives the same charge rate of 1.8 C. Peaks can be clearly seen during charging at 4.1 V and 4.7 V, which can

And

Indicates the presence of both. From this, the composition

(here

Was estimated to produce an oxygen defect LMNO having a value between 0 and 0.5).

이고, 이는

에 대해 이론적 용량의 36%이다.19 shows the corresponding discharge curve. From this, the discharge capacity for this half cell of LMNO versus Li in the liquid electrolyte is 53

, Which is

For 36% of theoretical capacity.

및 100 nm의 백금으로 코팅되고 증착에 걸쳐서 350℃로 유지되는 사파이어 기판상에 리튬, 망간, 니켈 및 산소 소스들로부터 직접 증착되었고 적소의 열전쌍으로부터 모니터링된다. 리튬 붕규산염의 고체 상태 전해질은 225℃에서 리튬, 붕소, 실리콘 및 산소 소스들로부터 직접 증착되었다. 기판은 캐소드와 전해질의 증착 사이에서 제어 가능하게 냉각되었다.

애노드는 일단 다시 225℃에서 주석 및 산소 기상 소스로부터 직접 증착되었다. 이들 증착들은 동일한 진공 챔버 내에서 교대로 수행되었다.

층의 완성 다음 그리고 샘플이 실온(17℃)으로 냉각되면, 니켈 전류 컬렉터는 증착된다(PVD에 의해).Additionally, a full solid state cell with LMNO cathode deposited in accordance with an embodiment of the present invention at a substrate temperature of 350 ° C. was prepared and tested. This cell was completely deposited by physical vapor deposition. LMNO cathode is 10 nm

And deposited directly from lithium, manganese, nickel and oxygen sources on a sapphire substrate coated with 100 nm platinum and maintained at 350 ° C. throughout the deposition and monitored from the thermocouple in place. The solid state electrolyte of lithium borosilicate was deposited directly from lithium, boron, silicon and oxygen sources at 225 ° C. The substrate was controllably cooled between the deposition of the cathode and the electrolyte.

The anode was once deposited directly from the tin and oxygen gas source again at 225 ° C. These depositions were performed alternately in the same vacuum chamber.

Following completion of the layer and when the sample is cooled to room temperature (17 ° C.), a nickel current collector is deposited (by PVD).

Thus, all three cathode, electrolyte and anode layers were deposited directly from the vapor sources of their component elements using a substrate temperature range of only 125 ° C. throughout the deposition process. This represents approximately isothermal battery manufacturing, which in turn is very advantageous when compared to conventional thin film battery manufacturing techniques. Small adjustments to substrate temperature for each layer can allow deposition to be optimized for each material while still allowing a single manufacturing procedure to be used for the entire battery.

와 동일하다. 비록 LMNO가 이 예에서 350℃에서 증착되었지만, 150℃만큼 낮은 기판 온도에서 이런 방법을 사용하여 증착된 LMNO의 XRD는 막들이 결정화되는 것을 도시한다. 그러므로, 150℃에서 그리고 그 초과의 온도들에서 증착된 LMNO를 포함하는 박막 셀들이 성공적으로 생성될 수 있다는 것이 예상될 수 있다.FIG. 20 shows charge and discharge curves from CC / CV experiments on this cell in the first cycle form when cycled between 5.0 V and 3.0 V in the glove box. The initial discharge capacity in this case is as high as 62% of the theoretical capacity of the cathode, 40.9

Is the same as Although LMNO was deposited at 350 ° C. in this example, the XRD of LMNO deposited using this method at a substrate temperature as low as 150 ° C. shows that the films crystallize. Therefore, it can be expected that thin film cells comprising LMNO deposited at 150 ° C. and above temperatures can be produced successfully.

Experimental Results: Thermally Compatible Materials Stacking  Description of the thing

As mentioned above, a problem when manufacturing thin film batteries is a method of managing steps involving high temperatures, such as annealing to determine the cathode layer, when some of the component layers such as amorphous electrolyte should not be exposed to high temperatures. to be. In a single cell, this can sometimes be managed by depositing the layers in the proper order, such as by depositing and annealing the cathode layer prior to depositing the electrolyte on the cathode. However, since the likelihood of depositing all layers requiring heat treatment will typically decrease with the number of layers before depositing all the layers that need to be avoided, such a solution may be necessary. As the number increases, it becomes less valid. For example, stacking of two or more cells is not feasible because the cathodes of the second and any subsequent cells will have to be deposited over the electrolytes of the first and any other previous cells. Thus, fabrication of multiple layered thin film structures using conventional deposition techniques is very difficult and in some cases not possible.

The present invention provides a solution to this problem. The ability to perform isothermal or quasi-isothermal deposition of layers of various both crystalline and amorphous compounds allows many layers to be made without the manufacture of any layer that affects the characteristics and quality of any previous layer. The manufacture of many multilayer structures and devices is made possible.

및 100 nm의 백금이 코팅된 사파이어 기판상에 리튬, 망간 및 산소 소스들로부터 직접 증착되었다. 기판의 온도는 증착에 걸쳐 350℃로 유지되고, 이는 적소의 열전쌍에 의해 모니터된다. 그 다음, 리튬 붕규산염을 포함하는 고체 상태 전해질은 225℃의 기판 온도로 리튬, 붕소, 실리콘 및 산소 소스들로부터 직접 증착되었다.

애노드는 주석 및 산소 소스들로부터 직접 증착되었고, 기판은 다시 225℃로 유지된다. 니켈 전류 컬렉터는

층의 완성 다음 그리고 샘플이 실온(17℃)으로 냉각된 후 증착되었다(PVD에 의해). 이 다음, 제 2 셀들의 어레이가 증착되었고, 마스크에 의해 정의된 정렬이 뒤따른다. 각각에 대해, 제 2 LMO 캐소드는 350℃의 기판 온도로 제 1 셀의 니켈 전류 컬렉터 상에 리튬, 망간 및 산소 소스들로부터 직접 증착되었다. 그 다음 제 2 리튬 붕규산염 고체 전해질 층은 225℃의 기판 온도로 리튬, 붕소, 실리콘, 및 산소 소스들을 사용하여 엘리먼트들로부터 직접 증착되었다.

애노드는 일단 다시 225℃에서 주석 및 산소로부터 직접 증착되었고, 상단 니켈 전류 컬렉터는 샘플이 실온(17℃)으로 냉각된 후 증착되었다(PVD에 의해). 따라서, 상부 셀들은 하부 셀과 동일한 방식으로 증착되었고, 상부 셀들의 증착 프로세스는 준-등온 절차 내에서 작은 범위의 온도들로 인해 하부 셀들의 층들상에 해로운 효과를 가지지 않는다. 이들 증착들은 동일한 진공 챔버 내에서 교대로 수행되었다.To illustrate this, an array of cells was deposited. In addition to the cathode / electrolyte / anode / current collector structures described above, an array of additional cells was deposited on top. In this case, the cathode layers of the second cells were deposited directly over the current collector layer of the underlying cell. This produced a stack of materials with a second cell on top of the first cell. This structure is fully utilized with the deposition of component elements of various compounds directly from vapor sources on a substrate or previously deposited layer, with slight minor changes in temperature between the layers, using the physical vapor deposition method described above. Generated. Masking schemes were used to create the structure and define an array of second cells on top of a single underlying first cell. For the underlying cell, the first LMO cathode is 10 nm as cathode current collector.

And deposited directly from lithium, manganese and oxygen sources on a 100 nm platinum coated sapphire substrate. The temperature of the substrate is maintained at 350 ° C. throughout the deposition, which is monitored by a thermocouple in place. The solid state electrolyte comprising lithium borosilicate was then deposited directly from lithium, boron, silicon and oxygen sources at a substrate temperature of 225 ° C.

The anode was deposited directly from the tin and oxygen sources and the substrate was again maintained at 225 ° C. Nickel current collector

Following completion of the layer and the sample was cooled to room temperature (17 ° C.) and deposited (by PVD). Next, an array of second cells was deposited, followed by the alignment defined by the mask. For each, a second LMO cathode was deposited directly from lithium, manganese and oxygen sources on the nickel current collector of the first cell at a substrate temperature of 350 ° C. The second lithium borosilicate solid electrolyte layer was then deposited directly from the elements using lithium, boron, silicon, and oxygen sources at a substrate temperature of 225 ° C.

The anode was deposited directly from tin and oxygen once again at 225 ° C. and the top nickel current collector was deposited (by PVD) after the sample had cooled to room temperature (17 ° C.). Thus, the upper cells were deposited in the same manner as the lower cell, and the deposition process of the upper cells had no detrimental effect on the layers of the lower cells due to the small range of temperatures within the quasi-isothermal procedure. These depositions were performed alternately in the same vacuum chamber.

층(제 2 애노드) 및 제 2 니켈 전류 컬렉터 층은 D6에 의해 표시된다.21 (a) shows an SEM image of this two cell stack with various layers visible. The image shows the sapphire substrate D0 in the upper right corner, and two cells are deposited thereon. The platinum current collector layer is represented by D1. This layer is 100 nm thick and deposited as part of the substrate processing. The first cathode layer comprising the LMO is denoted by D2 and is 314 nm thick. The first solid state electrolyte layer comprising lithium borosilicate (LBSO) is represented by D4 and is 418 nm thick. The tin oxide layer anode is too thin (approximately 8 nm) to be explained by SEM and is therefore not shown. The nickel current collector and the secondary cathode layer, again LMO, are represented by D3. The second solid state electrolyte layer, again LBSO, is represented by D5, and finally, bound

The layer (second anode) and the second nickel current collector layer are represented by D6.

21 (b) shows a schematic of the SEM image, in order to better display the various layers. Different layers are labeled with their corresponding materials.

SEM images show layers of a clear and well-defined structure, indicating that the layer of stacked cells can be achieved using the method according to an embodiment of the present invention without significant collapse of the layers. This opens up the possibility of simple fabrication of multilayer and stacked devices. An important feature to note is the obvious interfaces between the layers resulting from the smooth surface that the present deposition method produces. This allows the use of thinner layers as the surface features do not protrude across the layers, which provides reduced material costs and reduced times for smaller devices, deposition and overall device fabrication.

(사파이어 기판),

(결정질 캐소드), 및 리튬 탄산염,

의 컴포넌트들이다. 참조 라인들은 다음과 같이 상이한 피크들을 나타내기 위하여 그래프 상에 포함된다: 백금(00-004-0802), 심볼 "^"; 니켈(00-004-0850), 심볼 "+"; 사파이어(

)(00-010-0173);

(00-035-0782), 심볼 "*"; 및

(00-022-1141) 심볼 "!". 결정질 리튬 탄산염은, 고체 상태 전해질이 공기에 노출될 때 발생하는 것으로 주의되고; 그러므로 이 데이터는 위에 놓인 애노드 및 전류 컬렉터들에 의해 보호되지 않은 고체 상태 전해질의 구역들로부터 발생한다.FIG. 22 shows a plot of X-ray diffraction data collected on the cell stack shown in FIG. 21. These results indicate that sequential deposition of one stack on another stack, including the deposition of an LMO cathode at 350 ° C. for 2 hours on an already existing cell with an amorphous electrolyte, does not cause crystallization of the solid state electrolyte. The only crystalline components observed (indicated by the peaks in the graph) are platinum (in substrate), nickel (current collectors),

(Sapphire substrate),

(Crystalline cathode), and lithium carbonate,

Are the components of. Reference lines are included on the graph to indicate different peaks as follows: platinum (00-004-0802), symbol "^"; Nickel (00-004-0850), symbol "+"; Sapphire(

) (00-010-0173);

(00-035-0782), symbol "*"; And

(00-022-1141) The symbol "!". It is noted that crystalline lithium carbonate occurs when the solid state electrolyte is exposed to air; This data therefore arises from zones of the solid state electrolyte which are not protected by the overlying anode and current collectors.

LMO is deposited at 350 ° C. in these two stack examples. However, X-ray diffraction measurements of LMO deposited at substrate temperatures as low as 150 ° C. show that the films are to be determined (see FIG. 7), and thus a thin film cell comprising an LMO deposited at temperatures of 150 ° C. or higher. It can be expected that this will cycle successfully. Similarly, the results presented above for LMNO show crystallization over a similar range of substrate temperatures, so this material can also be used for the cathode.

애노드(100)가 있다. 각각의 상부 셀(90B)은 니켈 전류 컬렉터(102), LMO 캐소드(104), LBSO 전해질(108),

애노드(108) 및 니켈 전류 컬렉터(110)를 포함한다.23 shows a schematic side view of two cell stacks to better illustrate the arrangement of the various layers. The stack 90 includes a lower cell 90A and an array of top cells 90B adjacent to each other on top of the lower cell 90A, all of which are arranged on the sapphire substrate 92, and the sapphire substrate ( The platinum coating of 92 forms a current collector layer 94. The lower cell 90A includes an LMO cathode 94, an LBSO electrolyte 98,

There is an anode 100. Each upper cell 90B includes a nickel current collector 102, an LMO cathode 104, an LBSO electrolyte 108,

An anode 108 and a nickel current collector 110.

화학물에 대응하는 방전 전위가 모두 3.75 V 미만이고, 셀이 6 V만큼 높은 전위로 충전될 때에도 용량이 4 V를 초과하지 않는 것이 관찰되는 것을 명확하게 알 수 있다. 셀들이 직렬로 연결될 때 전위가 단일 셀 전위들의 부가에 의해 증가되는 것이 잘 알려져 있다. 셀들이 직렬로 연결되는 경우 2개의 스택 셀에 대한 방전 곡선은 4 V를 초과하는 전위들에서 전달되는 용량의 상당 부분을 가진 단일 셀에 비교될 때 전위의 증가를 나타내고, 이에 의해 양쪽 셀들이 전체 전위에 기여하는 것을 제공하는 것을 나타낸다.FIG. 24 shows the discharge curves for two stack cells after charging to 7V (real curve) compared to the discharge curve (dashed curve) for a single cell charged to 6V. From these measurements, LMO / for a single cell

It can be clearly seen that the discharge potentials corresponding to the chemicals are all less than 3.75 V and the capacity does not exceed 4 V even when the cell is charged to a potential as high as 6 V. It is well known that the potential is increased by the addition of single cell potentials when the cells are connected in series. When the cells are connected in series, the discharge curves for the two stack cells show an increase in potential when compared to a single cell with a significant portion of the capacity delivered at potentials above 4 V, whereby both cells become full To provide a contribution to the potential.

Temperature

From the various results presented above, there is a substrate temperature range spanning about 170 ° C., about 180 ° C. to 350 ° C., whereby both amorphous lithium-containing oxide and oxynitride compounds and crystalline lithium-containing transition metal compounds are deposited. It can be seen that. Therefore, operation within this temperature range allows for the deposition of multiple layers of different materials in a single manufacturing process with little or no temperature control. Operation at a single temperature for all layers may be referred to as “isothermal”, while operation within a temperature range over about 170 ° C. or less may be considered as “quasi-isothermal”. This term is a reasonable explanation when the process is compared to the range of temperatures typically required to produce layers of these materials using conventional techniques. Amorphous compounds are generally prepared at room temperature (ie between 17 ° C. and 25 ° C.), while the temperatures for producing crystalline compounds by either or both of annealing and deposition on a high temperature substrate are typically at least 500 ° C. Thus, the range of 170 ° C. according to the present invention is typically “quasi-isothermal” when compared to known ranges of 475 ° C. or higher.

Of course, a range of temperatures less than 170 ° C. may be used, and the range is chosen to optimize the process as a whole. For example, a small temperature range of 25 ° C. or 50 ° C. places smaller demands on the heating component and requires less time between the substrate depositing different layers to reach each desired temperature. These benefits also apply, of course, to using a constant temperature for all layers. Larger ranges, such as 75 ° C., 100 ° C. or 150 ° C., are directed to keeping the temperature low for amorphous materials in order to save energy while using higher temperatures for crystalline materials to increase crystal size. It may be desirable. For example, some of the examples include a cathode deposited at 350 ° C. and an electrolyte deposited at 225 ° C. and provide a range of 75 ° C. FIG. Various ranges may also apply to other upper and lower temperatures.

Additional materials

,

,

,

(NCA) 및

, 및 애노드들로서 사용하기 위한

이다. 이들 재료들은 다른 애플리케이션들에 사용될 수 있지만, 다른 리튬 함유 전이 금속 산화물들은 가능하다.So far, the preparation of amorphous lithium borosilicate and nitrogen-doped lithium borosilicate and crystalline LMO and LMNO has been described in detail. However, the present invention is not limited to these materials, and the deposition process of component elements directly on a heated substrate is applicable to the production of other lithium containing oxide and oxynitride compounds. Further examples include compounds including lithium silicate and lithium borates, and other glass-forming elements such as germanium, aluminum, arsenic, and antimony. It can be expected that amorphous oxides and oxynitrides can be prepared by the methods according to the invention, because the chemicals of the binary oxides are expected to be very similar to the chemicals of the tertiary oxide / oxynitride glasses. Because it can. Similarly, the deposition process of component elements directly on a heated substrate is applicable to the production of other lithium containing transition metal oxides in crystalline form. Any transition metal or metals may be substituted for the manganese and manganese plus nickel embodiments discussed so far. The chemistry of the transition metals is sufficiently similar and predictable over the group in which crystalline material can be expected to be deposited at intermediate substrate temperatures using the method of the present invention for any lithium containing transition metal oxide of interest. Materials of particular interest for certain applications are intended for use as cathodes.

,

,

,

(NCA) and

For use as, and anodes

to be. These materials can be used for other applications, but other lithium containing transition metal oxides are possible.

Substrates

The experimental results presented herein relate to thin films deposited on titanium and platinum coated sapphire substrates and titanium and platinum coated silicon substrates. However, other substrates may be used if desired. Other suitable examples include metal substrates including quartz, silica, glass, sapphire, and foils, but one skilled in the art will understand that other substrate materials will also be suitable. Requirements for the substrate are that a suitable deposition surface is provided and can withstand the required heating; Otherwise the substrate material may be selected as desired with reference to the application in which the deposited compound is placed.

In addition, embodiments of the present invention are equally applicable to the deposition of component elements directly on a substrate surface and directly on one or more layers previously deposited or otherwise fabricated on the substrate. This is evident from the experimental results discussed above, where films were otherwise deposited on empty heated substrates, amorphous electrolyte layers were deposited on the cathode layer when fabricating sample batteries, and multiple layers were deposited on the stacked cells. It was successfully deposited when indicated. Thus, in this application, references to "substrate", "deposit on substrate", "co-deposition on substrate" similarly refer to "substrate supporting one or more prefabricated layers", "substrate on substrate" The same applies to " deposition on a layer or layers fabricated in " &quot;, &quot; co-deposition on a layer or layers previously fabricated on a substrate. &Quot; The present invention applies equally whether or not there are any other layers interposed between the substrate and any particular amorphous or crystalline layer to be deposited.

Applications

The ability of the methods of the present invention to form both amorphous and crystalline thin film materials, combined with properties such as good ionic conductivity, smooth surface morphology, and good charge and discharge capacities allows the materials to be used as electrolytes and electrodes in thin film batteries. It is very suitable to do this, which is expected to be the main application. The methods of the present invention are readily adaptable to the manufacture of battery components in devices such as sensors, photovoltaic cells and integrated circuits, etc., in which both single cells and stacked cells are provided. However, the materials are not limited to using as battery components, and the method can be used to deposit layers of amorphous lithium-containing oxide or oxynitride compounds and crystalline lithium-containing transition metal oxides for any other applications. Possible examples include ionic conductors in sensors, lithium separators, interface modifiers, and electrochemical devices.

Further, the thin films can be deposited according to the invention in adjacent arrangements rather than layered arrangements.

References

[1] Tang, S.B., et al., J. Solid State Chem., 179 (12), (2006), 3831-3838

[2] Julien, C.M. and G.A. Nazri, Chapter 4. Materials for electrolyte: Thin Films, in Solid State Batteries: Materials Design and Optimization (1994)

[3] Thornton, J.A. and J.E. Greene, Sputter Deposition Processes, in Handbook of Deposition Technologies for films and coatings, R.F. Bunshah, Editor 1994, Noyes Publications

[4] Wang et al. Electrochimica Acta 102 (2013) 416-422

[5] WO 2013/011326

[6] WO 2013/011327

[7] Singh et al. J. Power Sources 97-98 (2001), 826-831

[8] Jayanth et al. Appl Nanosci. (2012) 2: 401-407

[9] Baggetto et al., J Power Sources 211 (2012) 108-118

[10] Zhong, Q., et al., J. Electrochem. Soc., (1997), 144 (1), 205-213

[11] Bates et al. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. Journal of Solid State Chemistry 1995, 115, (2), 313-323

[12] WO 2001/73883

[13] EP 1,305,838

[14] Julien, C. M .; Nazri, G. A., Chapter 1. Design and Optimization of Solid State Batteries. In Solid State Batteries: Materials Design and Optimization, 1994

[15] Bates, J. B .; Gruzalski, G. R .; Dudney, N. J .; Luck, C. F .; Yu, X., Rechargeable Thin Film Lithium Batteries. Oak Ridge National Lab and Solid State Ionics 1993

[16] US 5,338,625

Glasses. Yogyo-Kyokai-Shi 1987, 95, (2), 197-201[17] Tatsumisago, M .; Machida, N .; Minami, T., Mixed Anion Effect in Conductivity of Rapidly Quenched

Glasses. Yogyo-Kyokai-Shi 1987, 95, (2), 197-201

and

by RF-sputtering and their ionic conductivity. Yogyo-Kyokai-Shi 1987, 95, (1), 135-7[18] Machida, N .; Tatsumisago, M .; Minami, T., Preparation of amorphous films in the systems

and

by RF-sputtering and their ionic conductivity. Yogyo-Kyokai-Shi 1987, 95, (1), 135-7

[19] Varshneya, A. K., Fundamentals of Inorganic Glasses, Academic Press, page 33

[20] Guerin, S. and Hayden, B. E., Journal of Combinatorial Chemistry 8, 2006, pages 66-73

[21] WO 2005/035820

[22] Park, Y. J. et al., J. Power Sources, 88, (2000), 250-254

Claims (35)

A vapor deposition method for preparing a multi-layer thin film structure,
Providing a plurality of vapor sources of a compound element intended for a first layer and a component element of a compound intended for a second layer, each of the plurality of vapor sources comprising only one component element of the compounds, The plurality of vapor sources comprises at least a lithium source, an oxygen source, a source or sources of one or more glass-forming elements, and a source or sources of one or more transition metals;
Heating the substrate to a first temperature;
Co-depositing component elements from gaseous sources of at least said lithium, oxygen and said one or more said transition metals on said heated substrate, said component elements being a layer of a crystalline lithium-containing transition metal oxide compound Reacting on the substrate to form a;
Heating the substrate to a second temperature; And
Co-depositing component elements from at least lithium, oxygen and gaseous sources of the one or more glass-forming elements on the heated substrate, wherein the component elements are formed of an amorphous lithium-containing oxide or oxynitride compound. Reacting on the substrate to form a layer;
Including,
The first temperature and the second temperature are within a temperature range of 170 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 1,
The layer of crystalline lithium-containing transition metal oxide compound is deposited before the layer of amorphous lithium-containing oxide or oxynitride compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 1,
The layer of amorphous lithium-containing oxide or oxynitride compound is deposited prior to the layer of crystalline lithium-containing transition metal oxide compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The temperature range is 180 ℃ to 350 ℃,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 150 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The first temperature is 350 ° C. and the second temperature is 225 ° C.,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The first temperature and the second temperature are the same,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 7, wherein
Wherein both the first temperature and the second temperature are 225 ° C.,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The source or sources of one or more transition metals comprise a manganese source and the crystalline lithium-containing metal oxide compound is lithium manganese oxide or the manganese source and nickel source and the crystalline lithium-containing metal oxide compound are lithium manganese nickel Oxide,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The source or sources of one or more transition metals may be scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, detnetium, ruthenium, rhodium, palladium, Each source comprising one or more of silver, cadmium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, palladium, gold and mercury,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The gaseous sources further comprise a source of nitrogen, and wherein the amorphous lithium-containing oxide or oxynitride compound is a lithium-containing oxynitride compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The source or sources of the one or more glass-forming elements comprise a boron source and a silicon source and the amorphous lithium-containing oxide or oxynitride compound is lithium borosilicate or one or more glass-forming elements Source or sources of boron include a boron source and a silicon source, the gaseous sources further comprise a nitrogen source, and the amorphous lithium-containing oxide or oxynitride compound is nitrogen-doped lithium borosilicate,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the amorphous lithium-containing oxide or oxynitride compound is lithium silicate, oxynitride lithium silicate, lithium borate or oxynitride lithium borate
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
The source or sources of the one or more glass-forming elements include one or more sources of boron, silicon, germanium, aluminum, arsenic and antimony,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to claim 1 or 2,
Wherein the layer of amorphous lithium-containing oxide or oxynitride compound is deposited on the layer of crystalline lithium-containing transition metal oxide compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the layer of crystalline lithium-containing transition metal oxide compound is deposited to form a cathode of a thin film battery and the layer of amorphous lithium-containing oxide or oxynitride compound is deposited to form an electrolyte of a thin film battery,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Further comprising forming one or more additional layers on the layer of the crystalline lithium-containing transition metal oxide compound and / or the layer of the amorphous lithium-containing oxide or oxynitride compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 17,
At least one additional layer is formed on the substrate by co-depositing the component elements of the compound from the vapor sources of each component element of the compound intended for the additional layer, the component elements for the additional layer. Reacting on the substrate to form a layer of the intended compound,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 18,
The substrate is heated to a third temperature when a third layer is formed, wherein the first temperature, the second temperature and the third temperature are within a temperature range of 170 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 19,
The first temperature, the second temperature and the third temperature are the same,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 17,
The layer of crystalline lithium-containing transition metal oxide compound is deposited to form a cathode of a thin film battery, the layer of amorphous lithium-containing oxide or oxynitride compound is deposited to form an electrolyte of a thin film battery, and the one Or further layers comprise at least the anode of the thin film battery,
Vapor deposition method for preparing a multi-layer thin film structure. The method of claim 17,
The layer of crystalline lithium-containing transition metal oxide compound is deposited to form a cathode of a first thin film battery, and the layer of amorphous lithium-containing oxide or oxynitride compound is deposited to form an electrolyte of the first thin film battery. And the one or more additional layers comprise at least an anode of the first thin film battery and a cathode, an electrolyte and an anode of a second thin film battery formed on the first thin film battery to form a battery stack. doing,
Vapor deposition method for preparing a multi-layer thin film structure. As a way to make a battery,
The method of claim 1, wherein the battery is used as a layer of a crystalline lithium-containing transition metal oxide compound and the cathode is a layer of an amorphous lithium-containing oxide or oxynitride compound. Comprising depositing an electrolyte,
How to make a battery. As a battery,
A cathode in the form of a layer of a crystalline lithium-containing transition metal oxide compound and an electrolyte in the form of a layer of an amorphous lithium-containing oxide or oxynitride compound, the cathode and the electrolyte according to any one of claims 1 to 3. Deposited using a vapor deposition method according to
battery. As an electronic device,
A battery having a cathode in the form of a layer of crystalline lithium-containing transition metal oxide compound and an electrolyte in the form of an amorphous lithium-containing oxide or oxynitride compound layer, wherein the cathode and the electrolyte are any one of claims 1 to 3. Deposited using a vapor deposition method according to claim
Electronic device. As a sample,
A layer of crystalline lithium-containing transition metal oxide and a layer of amorphous lithium-containing oxide or oxynitride compound deposited on a substrate using a vapor deposition method according to any one of claims 1 to 3,
Sample. As a battery stack,
A cathode and an amorphous lithium-containing oxide comprising a first thin film cell and at least one second thin film cell stacked on the first thin film cell, each thin film cell comprising a layer of a crystalline lithium-containing transition metal oxide compound Or an electrolyte comprising a layer of an oxynitride compound, wherein the cathode and the electrolyte are deposited using a vapor deposition method according to any one of claims 1 to 3,
Battery stack. The method of claim 27,
Wherein the crystalline lithium-containing transition metal oxide compound comprises lithium manganese oxide or lithium manganese nickel oxide,
Battery stack. The method of claim 27,
Wherein the amorphous lithium-containing oxide or oxynitride compound comprises lithium borosilicate or nitrogen-doped lithium borosilicate,
Battery stack. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 100 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 75 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 50 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 25 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 10 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure. The method according to any one of claims 1 to 3,
Wherein the first and second temperatures are in the range of 5 ° C. or less,
Vapor deposition method for preparing a multi-layer thin film structure.

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